Based on survey data collected in 2016 from 100 villages across five provinces in China, this paper uses binary logistic model to explore the main factors related to the supply and quality of rural residential solid waste collection (RRSWC) services, especially focusing on the role of village population structure characteristics. It is indicated from the results that village population structure characteristics are significantly correlated with RRSWC services; specifically: (1) the total registered population of village households is significantly positively correlated with the supply of RRSWC services, however, the correlation between the registered population and the quality of RRSWC services is negative and the more the labors working and living outside the village, the less likely the village is to provide RRSWC services; (2) the villagers’ educational levels and RRSWC services show no significant correlativity at the present stage; (3) the preferential policies brought by population structure advantage play a positive role in the supply of RRSWC services but is not clearly related to the quality of RRSWC services, especially in the villages with a larger minority population. In addition, the study finds that, the economic development level of a village and the characteristics of village leaders are also positively correlated with the supply and quality of RRSWC services and; the natural and traffic conditions have no significant correlation with RRSWC services. This study can act as a reference for the further promotion of the development of RRSWC services in China.