Exploring the establishment of a payment system for household waste disposal is an effective way to relieve government pressure at all levels on the supply of public goods for the centralized disposal service of household waste. It is of great significance to the continuous improvement of rural residential environment and the construction of ecologically livable and beautiful countryside. Based on a survey data of households in Hubei and Henan provinces, this paper analyzed households’ willingness to pay for the centralized disposal service of household waste and explored the impacts of responsibility cognition and social capital on households’ willingness to pay by the Ordered Probit model. Results show that 48.53% of the sample households are unwilling to pay for the centralized disposal service. Among the households who are willing to pay, the level of willingness is 10 to 19 yuan per month. Responsibility cognition motivates households’ willingness to pay through content cognition and consequence cognition. In addition to interpersonal trust, strong relationship network, weak relationship network, institutional trust, social support, and social needs in social capital have positive impacts. While strong relationship network and social support play a positive moderating role between consequence cognition and households’ willingness to pay and weak relationship network, institutional trust and social needs play a positive moderating role between content cognition and households’ willingness to pay. Therefore, to effectively promote households’ participation in the centralized disposal survice of household waste, this paper suggests: to improve the level of households’ responsibility cognition, to strengthen accumulation of multi-dimensional social capital, to perfect the working mechanism to give a full play to the significant advantages of social capital in organization and operation.