The high-quality development of urban–rural buses is an important way to narrow the gap between urban and rural areas. However, studies on the quality of bus services and its impact on bus travel-mode choice have mostly focused on urban buses, with less attention paid to urban–rural buses. This paper aims to explore how urban–rural bus service quality affects rural residents’ travel-mode-choice behavior based on survey data from rural residents in Henan Province, China. A structural equation model (SEM) is applied to examine the critical factors affecting rural residents’ satisfaction with urban–rural bus service quality and the heterogeneity of satisfaction among rural residents with different attributes. Furthermore, an integrated approach of SEM and the multinomial logit (MNL) model is proposed to identify the key factors that affect rural residents’ bus travel-mode choice. The results indicate that reliability and convenience are the key factors affecting satisfaction with urban–rural bus service quality. There are significant differences in rural residents’ satisfaction by gender, age, income, education level, occupation, and travel-mode attributes. Urban–rural bus service quality has a significant positive impact on rural residents’ bus travel-choice behavior, and its degree of influence is greater than all explicit variables except private car ownership. The findings of this study can help operators and governments formulate policies to improve the service quality of urban–rural buses and ultimately promote the use of buses.