【Objective】 Intercropping is an effective strategy for increasing soil carbon (C) sequestration by utilizing farmland biodiversity. The aim of this study was to investigate the contribution of peanut rhizosphere microbes adjacent to maize to soil organic C (SOC) sequestration in an intercropping system. 【Method】 Based on the long-term peanut/maize intercropping experimental platform of Jiangsu Academy of Agricultural Sciences, two rows of peanuts and two rows of maize were planted in strips. Ecological test plate (BIOLOG) and gas chromatography were used to analyze the C metabolic ability of maize to adjacent peanuts rhizosphere microbes and the accumulation of microbial necromass C. 【Result】 The results showed that compared with peanuts planted far away from maize, peanuts planted adjacent to the maize decreased rhizosphere polyphenol oxidase activity by 19.0%, soil respiration rate by 18.2%, average color change rate (AWCD) by 22%, rhizosphere microbial metabolism of phenolic acids and amino acids by 149.4% and 16.1%, respectively. The total amino sugar ( TAS ) content of peanut rhizosphere soil adjacent to maize was 6.45% higher than that of peanut planted far away from maize, and the content of bacterial necromass C and fungal necromass C was increased, which eventually led to a 12.9% increase in SOC. 【Conclusion】 Our study suggests that adjacent maize does not change the soil respiration rate of the peanut rhizosphere, but reduces the activity of SOC decompositiong enzymes in the peanut rhizosphere and enhances the ability of rhizosphere microbes to metabolize a wider range of organic carbon components, thereby increasing SOC by accumulating bacterial and fungal necromass C.