Anaerobic digestion (AD) is a sustainable and widely adopted technology for the treatment of organic solid wastes (OSWs). However, AD efficiency varies significantly across different substrates, primarily due to differences in the microbial community and metabolic pathways. This review provides a comprehensive summary of the AD processes for four types of typical OSWs (i.e., sewage sludge, food waste, livestock manure, and straw), with an emphasis on their universal characteristics across global contexts, focusing mainly on the electron transfer mechanisms, essential microbial communities, and key metabolic pathways. Special attention was given to the mechanisms by which substrate-specific structural differences influence anaerobic digestion efficiency, with a focused analysis and discussion on how different components affect microbial communities and metabolic pathways. This study concluded that the hydrogenotrophic methanogenesis pathway, TCA cycle, and the Wood–Ljungdahl pathway serve as critical breakthrough points for enhancing methane production potential. This research not only provides a theoretical foundation for optimizing AD efficiency, but also offers crucial scientific insights for resource recovery and energy utilization of OSWs, making significant contributions to advancing sustainable waste management practices.