diff --git a/CHANGES b/CHANGES
index 6434cc3a7..2f6ff83a9 100644
--- a/CHANGES
+++ b/CHANGES
@@ -108,6 +108,8 @@ Bugs fixed
 * #5248: LaTeX: Greek letters in section titles disappear from PDF bookmarks
 * #5772: LaTeX: should the Bjarne style of fncychap be used for English also
   if passed as language option?
+* #5179: LaTex: (lualatex only) escaping of ``>`` by ``\textgreater{}`` is not
+  enough, ``\textgreater{}\textgreater{}`` applies TeX-ligature
 
 Testing
 --------
diff --git a/sphinx/writers/latex.py b/sphinx/writers/latex.py
index 7eb0317d9..c656fe6a3 100644
--- a/sphinx/writers/latex.py
+++ b/sphinx/writers/latex.py
@@ -207,7 +207,8 @@ ADDITIONAL_SETTINGS = {
         'latex_engine': 'lualatex',
         'polyglossia':  '\\usepackage{polyglossia}',
         'babel':        '',
-        'fontenc':      '\\usepackage{fontspec}',
+        'fontenc':     ('\\usepackage{fontspec}\n'
+                        '\\defaultfontfeatures[\rmfamily,\sffamily]{}'),
         'fontpkg':      LUALATEX_DEFAULT_FONTPKG,
         'textgreek':    '',
         'utf8extra':   ('\\catcode`^^^^00a0\\active\\protected\\def^^^^00a0'