The recent progress of multifunctional catalysts, such as microbes, bacterium, enzymes, microelements, adsorbents, foaming agents, chelating agents, dyes, inhibitors and so on, used in the anaerobic fermentation was reviewed. This paper also emphasized the roles of the biocatalysts in the process of anaerobic fermentation, discussed the several critical issues in the fermenting methane bacterium, process control, waste disposal using a systematic processing and highlighted the advantages of the use of catalysts for fermenting methane. Also, the perspective of the biocatalysts in anaerobic fermentation was given. The biogas production can not only make biomass resources deeply developed and recycled, but also cause the waste harmlessly treated and effectively utilized, transforming the trash into treasure and making the harm to benefit, which are of great practical significance to solve the present energy crisis and environmental pollution problems.