Carbofuran (CAS) is one of extensively used carbamate pesticides, which is considered as a derivative or a candidate of carbofuran (CAN) for its lower toxicity and persistence. Nevertheless, CAS could be degraded into its toxic metabolites, imposing potential risks on ecological safety. In this paper, biochars, derived from rice straw (RS), chicken manure (CM), corn straw (CS) and tire rubber (TR), were applied in CAS-contaminated soil to explore their effects on the dissipation of CAS and its metabolites. The dissipation rate of CAS was depressed by the amendment of biochar, mainly because biochar inhibited the hydrolysis of CAS by elevating soil pH value. Nevertheless, CS has efficiently enhanced the dissipation of CAN by almost 2-times for its promotion in hydrolysis and biodegradation. CS and CM improved biodegradation by altering the composition and structure of the microbial communities, exhibiting potential for facilitating bioremediation of CAS and CAN. Moreover, steam activated biochar accelerated the dissipation rate by 1.7–2.9 times and 1.3–2.4 times for CAS and CAN, respectively. This study investigated the effects of biochar on CAS and its toxic metabolites as well as possible governing mechanisms, providing rational instruction for biochar application in ambient atmosphere.