Abstract: The redox-active functional groups of soil humic substances (HS) can continuously transfer electrons from microorganisms to oxygen in continuous anoxic and aerobic alternations. Therefore, HS is essential for regulating the methane cycle in the temporary anoxic system. Land-use types could affect the electron transferability of soil HS. However, it remains unclear whether the land-use types would affect the sustainability of HS as the extracellular electron shuttle. In this study, we combined the cycle test of microbial reduction and oxygen re-oxidation to evaluate the response of soil humic acid (HA) and fulvic acid (FA) sustainability as the extracellular electron shuttle to different types of land use. The results showed that HS sustainability as the extracellular electron shuttle did not differ significantly between Shewanella oneidensis MR-1 and Shewanella putrefaciens 200 microbial systems, although significant differences could be observed among the land-use types of paddy (ST), grapevine (PT), and myrica rubra (YM). The HA sustainability as an extracellular electronic shuttle in ST, PT, and YM was 75.9%, 80.5% and 72.1%, respectively. The FA sustainability as an extracellular electronic shuttle was 58.2%, 62.2% and 62.9%, respectively. These results might be due to different types of land use, resulting in different soil HS composition, decomposition, and transformation processes, and different dynamic processes driven by microbial electron donor carbon sources. Our results showed that the sustainability of soil HS as an extracellular electronic shuttle was significantly different among the different types of land use, and HA sustainability as an extracellular electronic shuttle was obviously greater than that of FA. Therefore, the degradation and transformation of soil pollutants could be achieved by improving the environmental control measures to form HA.