There is global enthusiasm for payments for ecosystem services (PES) programs to solve environmental problems, including in China. However, PES programs in China go against the principle of ‘voluntary transaction’, which weakens the influences of economic factors on farmers’ participation decisions and makes it hard to reveal their influence on farmers’ participation willingness. Using household survey data and a logistic regression model, this study attempts to understand the influencing factors of farmers’ decision-making on involvement in PES projects for hypothetical voluntary participation and focuses on whether the farmer would reject the program if the payment stopped. A surprising but promising result is found in the case of the Paddy Landto-Dry Land (PLDL) program in Chicheng County, China, wherein, apart from the negative impact of education and the positive effect of off-farm income, two non-economic factors play a significant role in farmers’ participation. The one is basic cognition, which negatively affects farmers’ participation, and the other is inner altruistic motivation, which positively contributes to the participation. In addition, the high proportion of reconversion to paddy land after the payment period threatens the long-term sustainability of the PLDL program. Faced with the low education and environmental cognition statuses in remote agricultural areas, increasing educational quality and promoting the popular awareness of PES programs in rural areas should be highlighted in sustaining the efficiency and effectiveness of PES programs in the long run.