Anaerobic digestion using lignocellulosic material as the substrate is a cost-effective strategy for biomethane production, which provides great potential to convert biomass into renewable energy. However, the recalcitrance of native lignocellulosic biomass makes it resistant to microbial hydrolysis, which reduces the bioconversion efficiency of organic matter into biogas. Therefore, it is necessary to critically investigate the correlation between lignocellulose characteristics and bioconversion efficiency. Accordingly, this review comprehensively summarizes the anaerobic digestion process and rate-limiting step, structural and compositional properties of lignocellulosic biomass, recalcitrance and inhibitors of lignocellulose and their major effects on anaerobic digestion for biomethane production. Moreover, various type of pretreatment strategies applied to lignocellulosic biomass was discussed in detail, which would contribution to cell wall degradation and improvement of biomethane yields. In the view of current knowledge, high energy input and cost requirements are the main limitations of these pretreatment methods. In addition to optimization of fermentation process, further studies should focus much more on key structural influence factors of biomass recalcitrance and anaerobic digestion efficiency, which will contribute to improvement of biomethane production from lignocellulose.