Introduction: The deviation between the stated intentions and actual actions of rural residents regarding waste classification constitutes a significant impediment to the effective implementation of environmental management strategies in rural areas. It is therefore recommended that steps be taken to reduce the deviation between the stated intentions and actual behaviors of rural residents. Doing so will help to reinforce environmental governance in rural communities and provide the necessary support for rural revitalization.Methods: This study establishes an analytical framework for examining the deviation between the internal perceived efficacy and external environmental policies among rural residents. The relationship between intention and behavior can be classified into three distinct scenarios: “intention with behavior,” “intention without behavior,” and “no intention with behavior.” Furthermore, an empirical analysis is conducted using survey data collected by Nanjing Agricultural University in the China Land Economic Survey in June and July 2021.Result: The results show that 1) the perceived efficacy has a significant positive influence on the deviation between the intention and behavior of rural residents in domestic waste classification, while the environmental policy has a significant negative effect on it; 2) the guiding policy has a significant negative moderating effect on the influence of perceived efficacy on the deviation between the intention and behavior of rural residents and the situation of “with intention and without behavior,” while the reward–punishment policy has a significant positive moderating effect on the influence of perceived efficacy on “without intention and behavior;” 3) the perceived efficacy has a masking effect on the impact of environmental policies on the deviation between the intention and behavior or “with intention and without behavior” of rural residents and a partial mediating effect on the impact of the environmental policy on “with intention and behavior” or “without intention and behavior.”Discussion: In consideration of these findings, the study proposes policy recommendations that emphasize the interconnectivity of the government, village collective organizations, and rural residents. The recommendations include the implementation of environmental policies and initiatives designed to enhance rural residents’ awareness of waste classification.