<P><B>Summary</B></P><P><I>p</I>‐Coumaroyl ester 3‐hydroxylase (C3′H) is a key enzyme involved in the biosynthesis of lignin, a phenylpropanoid polymer that is the major constituent of secondary cell walls in vascular plants. Although the crucial role of C3′H in lignification and its manipulation to upgrade lignocellulose have been investigated in eudicots, limited information is available in monocotyledonous grass species, despite their potential as biomass feedstocks. Here we address the pronounced impacts of <I>C3</I>′<I>H</I> deficiency on the structure and properties of grass cell walls. <I>C3</I>′<I>H</I>‐knockdown lines generated via RNA interference (RNAi)‐mediated gene silencing, with about 0.5% of the residual expression levels, reached maturity and set seeds. In contrast, <I>C3</I>′<I>H</I>‐knockout rice mutants generated via CRISPR/Cas9‐mediated mutagenesis were severely dwarfed and sterile. Cell wall analysis of the mature <I>C3</I>′<I>H</I>‐knockdown RNAi lines revealed that their lignins were largely enriched in <I>p</I>‐hydroxyphenyl (H) units while being substantially reduced in the normally dominant guaiacyl (G) and syringyl (S) units. Interestingly, however, the enrichment of H units was limited to within the non‐acylated lignin units, with grass‐specific γ‐<I>p</I>‐coumaroylated lignin units remaining apparently unchanged. Suppression of <I>C3</I>′<I>H</I> also resulted in relative augmentation in tricin residues in lignin as well as a substantial reduction in wall cross‐linking ferulates. Collectively, our data demonstrate that <I>C3</I>′<I>H</I> expression is an important determinant not only of lignin content and composition but also of the degree of cell wall cross‐linking. We also demonstrated that <I>C3</I>′<I>H</I>‐suppressed rice displays enhanced biomass saccharification.</P><P><B>Significance Statement</B></P><P>Suppression of a gene encoding <I>p</I>‐coumaroyl ester 3‐hydroxylase in rice resulted in altered lignins largely enriched in <I>p</I>‐hydroxyphenyl units, augmentation of tricin residues in lignin, and substantial reduction in wall cross‐linking ferulates. Such structural alterations reduced cell wall recalcitrance and enhanced cell wall saccharification to produce fermentable sugars from rice lignocellulose.</P>