The aromatic composition of lignins is considered an important trait that affects the physico-chemical properties of lignocellulosic biomass. However, our knowledge of the relationship between lignin structure and biomass utilization properties remains limited, especially in monocotyledonous grass species, despite their potential as biomass feedstocks. In this study, we used recently produced rice transgenic lines with distinct lignin monomer compositions, i.e., guaiacyl (G)/syringyl (S)/p-hydroxyphenyl (H) aromatic unit ratios, to study the impact of lignin composition on the chemical reactivity, enzymatic saccharification efficiency and calorific value of rice lignocellulose. The H-ligninenriched rice transgenic line showed significantly enhanced biomass saccharification efficiency after alkali and acid pretreatments and even without any pretreatment, whereas the S-lignin-enriched rice transgenic line displayed enhanced saccharification efficiency after liquid hot water pretreatment. While we detected no significant differences in biomass heating values between the transgenic rice materials tested, analysis of synthetic lignins comprising only G, S or H units suggested that increased ratios of G or H units could increase the heating value of lignin-based solid biofuels.