Agricultural extension services play an important role in promoting pesticide reduction and green production, although the mismatch between farmers’ needs and service supply in rural China seriously affects the application and promotion of biological pesticides, which has been generally ignored by existing studies. Taking 1160 rice farmers in Hubei Province, China, as an example, this study constructs a need-supply fit model of agricultural extension services from the perspectives of need and supply. We further use the logit model and propensity score matching method (PSM) to estimate the effect of service need-supply fit on farmers’ biological pesticide adoption behavior. The specific results are as follows: First, the level of need-supply fit for agricultural extension services was low for the overall sample. This indicates that the agricultural extension service supply is not consistent with the actual needs of farmers. Second, the agricultural extension service need-supply fit significantly and positively affects farmers’ biological pesticide adoption behavior. Third, there are significant differences in farmers’ biological pesticide adoption behaviors under different need-supply fit. When the level of service need-supply fit exceeds the 0.2 threshold, the positive effect of service need-supply fit on farmers’ biological pesticide adoption behavior gradually increases. Fourth, the agricultural extension service need-supply fit indirectly increases farmers’ motivation to adopt biological pesticides by regularizing biological pesticide use behavior and alleviating path dependency. Therefore, the main body of agricultural extension services should optimize the adjustment of the supply mode of agricultural extension services to fully grasp the reality of farmers’ need for biological pesticides in order to promote the application of biological pesticides.