diff --git a/CHANGES b/CHANGES
index d52b5e70b5f..9123a0f7667 100644
--- a/CHANGES
+++ b/CHANGES
@@ -19,8 +19,8 @@ Bugs fixed
 * #10594: HTML Theme: field term colons are doubled if using Docutils 0.18+
 * #10596: Build failure if Docutils version is 0.18 (not 0.18.1) due
   to missing ``Node.findall()``
-* #10506: LaTeX: build error when using ``:cpp:stuff`` syntax highlighting in
-  figure caption
+* #10506: LaTeX: build error if highlighting inline code role in figure caption
+  (refs: #10251)
 
 Testing
 --------
diff --git a/sphinx/highlighting.py b/sphinx/highlighting.py
index b86c31f5e48..62f10f7a148 100644
--- a/sphinx/highlighting.py
+++ b/sphinx/highlighting.py
@@ -40,12 +40,39 @@
                    ord('}'): '\\PYGZcb{}'}
 
 # used if Pygments is available
+# MEMO: no use of \protected here to avoid having to do hyperref extras,
+# (if in future code highlighting in sectioning titles is activated):
+# the definitions here use only robust, protected or chardef tokens,
+# which are all known to the hyperref re-encoding for bookmarks.
+# The " is troublesome because we would like to use \text\textquotedbl
+# but \textquotedbl is *defined to raise an error* (!) if the font
+# encoding is OT1.  This however could happen from 'fontenc' key.
+# MEMO: the Pygments escapes with \char`\<char> syntax, if the document
+# uses old OT1 font encoding, work correctly only in monospace font.
+# MEMO: the Pygmentize output mark-up is always with a {} after.
 _LATEX_ADD_STYLES = r'''
-% Sphinx additions
-% use textcomp quote to get a true single quote
-\renewcommand\PYGZsq{\textquotesingle}
+% Sphinx redefinitions
+% Originally to obtain a straight single quote via package textcomp, then
+% to fix problems for the 5.0.0 inline code highlighting (captions!).
+% The \text is from amstext, a dependency of sphinx.sty.  It is here only
+% to avoid build errors if for some reason expansion is in math mode.
+\def\PYGZbs{\text\textbackslash}
+\def\PYGZus{\_}
+\def\PYGZob{\{}
+\def\PYGZcb{\}}
+\def\PYGZca{\text\textasciicircum}
+\def\PYGZam{\&}
+\def\PYGZlt{\text\textless}
+\def\PYGZgt{\text\textgreater}
+\def\PYGZsh{\#}
+\def\PYGZpc{\%}
+\def\PYGZdl{\$}
+\def\PYGZhy{\sphinxhyphen}% defined in sphinxlatexstyletext.sty
+\def\PYGZsq{\text\textquotesingle}
+\def\PYGZdq{"}
+\def\PYGZti{\text\textasciitilde}
 \makeatletter
-% use \protected to allow \PYG in \caption
+% use \protected to allow syntax highlighting in captions
 \protected\def\PYG#1#2{\PYG@reset\PYG@toks#1+\relax+{\PYG@do{#2}}}
 \makeatother
 '''
diff --git a/sphinx/texinputs/sphinxlatexstyletext.sty b/sphinx/texinputs/sphinxlatexstyletext.sty
index 539ee0de3ed..31378b76f73 100644
--- a/sphinx/texinputs/sphinxlatexstyletext.sty
+++ b/sphinx/texinputs/sphinxlatexstyletext.sty
@@ -1,7 +1,7 @@
 %% TEXT STYLING
 %
 % change this info string if making any custom modification
-\ProvidesFile{sphinxlatexstyletext.sty}[2021/12/06 text styling]
+\ProvidesFile{sphinxlatexstyletext.sty}[2022/07/02 text styling]
 
 % Basically everything here consists of macros which are part of the latex
 % markup produced by the Sphinx latex writer
@@ -68,6 +68,7 @@
     \let\sphinxcrossref \@firstofone
     \let\sphinxtermref  \@firstofone
     \let\sphinxhyphen\sphinxhyphenforbookmarks
+    \def\PYG#1#2{#2}% (can not yet appear in section titles, but perhaps in future)
 }}
 
 % Special characters