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The humic substances (HS) - mediated electron transfer process is of great significance to the reduction and degradation of pollutants and the improvement of soil quality. Different soil conditions lead to different characteristics of HS, resulting in differences in the electron transfer capacity (ETC) of HS. It is unclear how the environmental conditions in soil affect the ETC by affecting on HS. In this study, the response relationship of soil microenvironment, HS and ETC has been studied. The results show that the ETC follows the descending order of: Langshan > Nanchang > Anqing > Beijing > Guilin. There were significant differences in ETC in soil HS in different regions. There were significant differences in electron-donating capacity (EDC) in soil HS in different regions and depths. EDC in soil was higher than electron-accepting capacity (EAC), and on average, are 22.4 times higher than the EAC. The HS components of soils in different regions are different. The most significant differences were in tyrosine-like substances and soluble microbial by-products (SMPs). The five components of the soil HS from Langshan were the most different from those in other regions. There were differences in SMPs and humic-like substances in soils of different depths in Anqing and Guilin. ETC can be affected by the composition of HS components in different regions. The composition of HS at different soil depths in the same regions had little effect on ETC. SMPs can promote ETC and EDC, and tyrosine-like substance can promote EDC. Moisture content, pH and TOC are the main factors affecting the composition of HS components. This results can provide a research basis for the sustainable and safe utilization of agricultural soil. [ABSTRACT FROM AUTHOR]