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Strengthening direct interspecies electron transfer (DIET), via adding conductive materials, is regarded as an effective way for improving methane productivity of anaerobic digestion (AD). Therein, the supplementation of combined materials (composition of biochar and iron-based materials) has attracted increasing attention in recent years, because of their advantages of promoting organics reduction and accelerating biomass activity. However, as far as we known, there is no study comprehensively summarizing the application of this kind combined materials. Here, the combined methods of biochar and iron-based materials in AD system were introduced, and then the overall performance, potential mechanisms, and microbial contribution were summarized. Furthermore, a comparation of the combinated materials and single material (biochar, zero valent iron, or magnetite) in methane production was also evaluated to highlight the functions of combined materials. Based on these, the challenges and perspectives were proposed to point the development direction of combined materials utilization in AD field, which was hoped to provide a deep insight in engineering application. [ABSTRACT FROM AUTHOR]