diff --git a/doc/source/_static/style/format_excel_css.png b/doc/source/_static/style/format_excel_css.png
new file mode 100644
index 0000000000000..0bd4662c3f2d0
Binary files /dev/null and b/doc/source/_static/style/format_excel_css.png differ
diff --git a/doc/source/whatsnew/v1.4.2.rst b/doc/source/whatsnew/v1.4.2.rst
index 9f4d248ca7042..badda6a73d1c8 100644
--- a/doc/source/whatsnew/v1.4.2.rst
+++ b/doc/source/whatsnew/v1.4.2.rst
@@ -16,6 +16,7 @@ Fixed regressions
 ~~~~~~~~~~~~~~~~~
 - Fixed regression in :meth:`DataFrame.drop` and :meth:`Series.drop` when :class:`Index` had extension dtype and duplicates (:issue:`45860`)
 - Fixed memory performance regression in :meth:`Series.fillna` when called on a :class:`DataFrame` column with ``inplace=True`` (:issue:`46149`)
+- Provided an alternative solution for passing custom Excel formats in :meth:`.Styler.to_excel`, which was a regression based on stricter CSS validation. Examples available in the documentation for :meth:`.Styler.format` (:issue:`46152`)
 -
 
 .. ---------------------------------------------------------------------------
diff --git a/pandas/io/formats/excel.py b/pandas/io/formats/excel.py
index 5371957365eae..98a87bfed7da9 100644
--- a/pandas/io/formats/excel.py
+++ b/pandas/io/formats/excel.py
@@ -316,7 +316,9 @@ def build_fill(self, props: Mapping[str, str]):
             return {"fgColor": self.color_to_excel(fill_color), "patternType": "solid"}
 
     def build_number_format(self, props: Mapping[str, str]) -> dict[str, str | None]:
-        return {"format_code": props.get("number-format")}
+        fc = props.get("number-format")
+        fc = fc.replace("§", ";") if isinstance(fc, str) else fc
+        return {"format_code": fc}
 
     def build_font(
         self, props: Mapping[str, str]
diff --git a/pandas/io/formats/style_render.py b/pandas/io/formats/style_render.py
index 0b3500cb34f87..9c62dd4072d3f 100644
--- a/pandas/io/formats/style_render.py
+++ b/pandas/io/formats/style_render.py
@@ -992,6 +992,10 @@ def format(
         -------
         self : Styler
 
+        See Also
+        --------
+        Styler.format_index: Format the text display value of index labels.
+
         Notes
         -----
         This method assigns a formatting function, ``formatter``, to each cell in the
@@ -1027,6 +1031,12 @@ def format(
           - ``styler.format.thousands``: default None.
           - ``styler.format.escape``: default None.
 
+        .. warning::
+           `Styler.format` is ignored when using the output format `Styler.to_excel`,
+           since Excel and Python have inherrently different formatting structures.
+           However, it is possible to use the `number-format` pseudo CSS attribute
+           to force Excel permissible formatting. See examples.
+
         Examples
         --------
         Using ``na_rep`` and ``precision`` with the default ``formatter``
@@ -1094,6 +1104,19 @@ def format(
         1 & \textbf{\textasciitilde \space \textasciicircum } \\
         2 & \textbf{\$\%\#} \\
         \end{tabular}
+
+        Pandas defines a `number-format` pseudo CSS attribute instead of the `.format`
+        method to create `to_excel` permissible formatting. Note that semi-colons are
+        CSS protected characters but used as separators in Excel's format string.
+        Replace semi-colons with the section separator character (ASCII-245) when
+        defining the formatting here.
+
+        >>> df = pd.DataFrame({"A": [1, 0, -1]})
+        >>> pseudo_css = "number-format: 0§[Red](0)§-§@;"
+        >>> df.style.applymap(lambda v: css).to_excel("formatted_file.xlsx")
+        ...  # doctest: +SKIP
+
+        .. figure:: ../../_static/style/format_excel_css.png
         """
         if all(
             (
@@ -1185,6 +1208,10 @@ def format_index(
         -------
         self : Styler
 
+        See Also
+        --------
+        Styler.format: Format the text display value of data cells.
+
         Notes
         -----
         This method assigns a formatting function, ``formatter``, to each level label
@@ -1211,6 +1238,13 @@ def format_index(
         When using a ``formatter`` string the dtypes must be compatible, otherwise a
         `ValueError` will be raised.
 
+        .. warning::
+           `Styler.format_index` is ignored when using the output format
+           `Styler.to_excel`, since Excel and Python have inherrently different
+           formatting structures.
+           However, it is possible to use the `number-format` pseudo CSS attribute
+           to force Excel permissible formatting. See documentation for `Styler.format`.
+
         Examples
         --------
         Using ``na_rep`` and ``precision`` with the default ``formatter``
diff --git a/pandas/tests/io/formats/test_to_excel.py b/pandas/tests/io/formats/test_to_excel.py
index 08ba05e7ab9ce..b95a5b4365f43 100644
--- a/pandas/tests/io/formats/test_to_excel.py
+++ b/pandas/tests/io/formats/test_to_excel.py
@@ -210,6 +210,10 @@
         ("white-space: normal", {"alignment": {"wrap_text": True}}),
         # NUMBER FORMAT
         ("number-format: 0%", {"number_format": {"format_code": "0%"}}),
+        (
+            "number-format: 0§[Red](0)§-§@;",
+            {"number_format": {"format_code": "0;[red](0);-;@"}},  # GH 46152
+        ),
     ],
 )
 def test_css_to_excel(css, expected):