We investigated the potential role of Fe-Mn-modified biochar composites (FMBCs) in the volatilization of toxic arsenic (As) in flooded paddy soil, by considering As fractionation, enzyme activities, and bacterial abundance. The results indicated that the addition of FMBCs reduced As volatilization from polluted soil, and this effect was more pronounced at higher dosages. Two types of FMBCs (i.e., FMBC1 and FMBC2) were analyzed, and FMBC2 exhibited a superior performance to FMBC1. Maximum volatilization was achieved in the fourth week and was followed by stabilization. In addition, the majority of As in the soil corresponded to crystalline and residual phases. Furthermore, the addition of FMBCs had little influence on the activities of various enzymes, although FMBC1 significantly affected catalase and peroxidase activities (P < 0.05). Moreover, FMBC application changed the relative abundances of different bacteria, where the abundances of Firmicutes were reduced, but a 2 g dose of FMBCs in highly polluted soil increased the bacterial abundance. In addition, the As volatilization, As fractionation, and enzyme activities displayed some correlation, in that As volatilization was negatively correlated to the presence of residual As phases but positively correlated to amorphous and poorly crystalline hydrous oxides of Fe and Al. As such, As fractionation and an improvement in soil properties are important mechanisms for reducing As volatilization.