Waste classification is an important part of the renovation of rural human settlements, and the renovation of rural human settlements is also of great significance to global sustainable development. Therefore, it is of the utmost importance to study the factors that affect the classification behavior for promoting waste classification behavior. However, few studies have focused on the political participation of rural residents as a driving factor. Therefore, this study aims to explore whether political participation affects rural residents’ waste classification behavior. In particular, this study uses the China Land Economic Survey (CLES), which surveyed 2628 rural households in Jiangsu Province, China, and uses the Probit model to explore the quantitative impact of political participation on farmers’ waste classification behavior. This study finds that: (1) Political participation may significantly improve farmers’ waste classification behavior. Specifically, farmers who participated in the general election were 10.6% more likely to conduct waste classification than those who did not vote in the general election. (2) Groups receiving government subsidies may be more likely to understand the government’s waste classification policy and then carry out waste classification. (3) Residents in areas with high economic development may be more sensitive to opportunity cost than residents in areas with low economic development, so residents in areas with high economic development degree are less willing to participate in waste classification action, and political participation has less influence on waste classification. Therefore, this research helps improve the efficiency of waste classification, ameliorate waste classification behavior, and provide the references for building a more civilized rural living environment.