diff --git a/piptools/utils.py b/piptools/utils.py
index 3065fee63..68a46f51d 100644
--- a/piptools/utils.py
+++ b/piptools/utils.py
@@ -2,6 +2,7 @@
 
 import collections
 import copy
+import difflib
 import itertools
 import json
 import os
@@ -561,6 +562,7 @@ def override_defaults_from_config_file(
 
     config = parse_config_file(config_file)
     if config:
+        _validate_config(ctx, config)
         _assign_config_to_cli_context(ctx, config)
 
     return config_file
@@ -576,6 +578,45 @@ def _assign_config_to_cli_context(
     click_context.default_map.update(cli_config_mapping)
 
 
+def _validate_config(
+    click_context: click.Context,
+    config: dict[str, Any],
+) -> None:
+    """
+    Validate parsed config against click command params.
+
+    :raises click.NoSuchOption: if config contains unknown keys.
+    :raises click.BadOptionUsage: if config contains invalid values.
+    """
+    cli_params = {
+        param.name: param
+        for param in click_context.command.params
+        if param.name is not None
+    }
+
+    for key, value in config.items():
+        # Validate unknown keys
+        if key not in cli_params:
+            possibilities = difflib.get_close_matches(key, cli_params.keys())
+            raise click.NoSuchOption(
+                option_name=key,
+                message=f"No such config key {key!r}.",
+                possibilities=possibilities,
+                ctx=click_context,
+            )
+
+        # Validate invalid values
+        param = cli_params[key]
+        try:
+            param.type.convert(value=value, param=param, ctx=click_context)
+        except Exception as e:
+            raise click.BadOptionUsage(
+                option_name=key,
+                message=f"Invalid value for config key {key!r}: {value!r}.",
+                ctx=click_context,
+            ) from e
+
+
 def select_config_file(src_files: tuple[str, ...]) -> Path | None:
     """
     Returns the config file to use for defaults given ``src_files`` provided.
@@ -614,6 +655,7 @@ def select_config_file(src_files: tuple[str, ...]) -> Path | None:
     "upgrade_package": "upgrade_packages",
     "resolver": "resolver_name",
     "user": "user_only",
+    "pip_args": "pip_args_str",
 }
 
 
diff --git a/tests/test_cli_compile.py b/tests/test_cli_compile.py
index edb4d2087..693054400 100644
--- a/tests/test_cli_compile.py
+++ b/tests/test_cli_compile.py
@@ -2989,3 +2989,31 @@ def test_no_config_option_overrides_config_with_defaults(
 
     assert out.exit_code == 0
     assert "Dry-run, so nothing updated" not in out.stderr
+
+
+def test_raise_error_on_unknown_config_option(
+    pip_conf, runner, tmp_path, make_config_file
+):
+    config_file = make_config_file("unknown-option", True)
+
+    req_in = tmp_path / "requirements.in"
+    req_in.touch()
+
+    out = runner.invoke(cli, [req_in.as_posix(), "--config", config_file.as_posix()])
+
+    assert out.exit_code == 2
+    assert "No such config key 'unknown_option'" in out.stderr
+
+
+def test_raise_error_on_invalid_config_option(
+    pip_conf, runner, tmp_path, make_config_file
+):
+    config_file = make_config_file("dry-run", ["invalid", "value"])
+
+    req_in = tmp_path / "requirements.in"
+    req_in.touch()
+
+    out = runner.invoke(cli, [req_in.as_posix(), "--config", config_file.as_posix()])
+
+    assert out.exit_code == 2
+    assert "Invalid value for config key 'dry_run': ['invalid', 'value']" in out.stderr
diff --git a/tests/test_cli_sync.py b/tests/test_cli_sync.py
index 0ebcddf8d..9eca78082 100644
--- a/tests/test_cli_sync.py
+++ b/tests/test_cli_sync.py
@@ -398,3 +398,29 @@ def test_no_config_option_overrides_config_with_defaults(run, runner, make_confi
 
     assert out.exit_code == 0
     assert "Would install:" not in out.stdout
+
+
+@mock.patch("piptools.sync.run")
+def test_raise_error_on_unknown_config_option(run, runner, tmp_path, make_config_file):
+    config_file = make_config_file("unknown-option", True)
+
+    with open(sync.DEFAULT_REQUIREMENTS_FILE, "w") as reqs_txt:
+        reqs_txt.write("six==1.10.0")
+
+    out = runner.invoke(cli, ["--config", config_file.as_posix()])
+
+    assert out.exit_code == 2
+    assert "No such config key 'unknown_option'" in out.stderr
+
+
+@mock.patch("piptools.sync.run")
+def test_raise_error_on_invalid_config_option(run, runner, tmp_path, make_config_file):
+    config_file = make_config_file("dry-run", ["invalid", "value"])
+
+    with open(sync.DEFAULT_REQUIREMENTS_FILE, "w") as reqs_txt:
+        reqs_txt.write("six==1.10.0")
+
+    out = runner.invoke(cli, ["--config", config_file.as_posix()])
+
+    assert out.exit_code == 2
+    assert "Invalid value for config key 'dry_run': ['invalid', 'value']" in out.stderr
diff --git a/tests/test_utils.py b/tests/test_utils.py
index 4820492d6..f06a42100 100644
--- a/tests/test_utils.py
+++ b/tests/test_utils.py
@@ -573,21 +573,16 @@ def test_get_sys_path_for_python_executable():
 @pytest.mark.parametrize(
     ("pyproject_param", "new_default"),
     (
-        # From sync
-        ("ask", True),
         ("dry-run", True),
         ("find-links", ["changed"]),
         ("extra-index-url", ["changed"]),
         ("trusted-host", ["changed"]),
         ("no-index", True),
-        ("python-executable", "changed"),
         ("verbose", True),
         ("quiet", True),
-        ("user", True),
         ("cert", "changed"),
         ("client-cert", "changed"),
         ("pip-args", "changed"),
-        # From compile, unless also in sync
         ("pre", True),
         ("rebuild", True),
         ("extras", ["changed"]),