In today’s increasingly competitive coffee industry, the point of running a good coffee shop is no longer to run a coffee and beverage shop simply, but to focus on the quality of service and the value that customers feel as a result. Previous studies have mainly discussed the customer satisfaction and behavioral intention of restaurants, while few studies have explored the influencing factors of customer satisfaction and behavioral intention of chain coffee shops. Given that the perceived service quality theory and DINESERV model can effectively predict customer satisfaction and behavioral intention, this study took 385 consumers in the first Starbucks Reserve flagship store in China as survey objects. SmartPLS 3.0 software was used to explore the relationship among respondents’ perceived service quality, customer perceived value, satisfaction, and behavioral intention. The results show that service quality has a partially significant positive effect on perceived value. Perceived service quality and customers’ perceived value both have significant positive effects on satisfaction. Customers’ satisfaction has a significant positive effect on their behavioral intention. These results indicate that enterprises should strengthen the emotional bond between consumers and enterprises and improve the reliability, assurance, and empathy of perceived service quality to create a better emotional resonance between consumers and the Starbucks brand to improve customer satisfaction. At the same time, it should also promote the symbolic perceived value of Chinese consumers to Starbucks to realize the sustainable development of coffee-shop operation and consumer repurchase. This study expands the research on the service quality, perceived value, and behavioral intention of coffee chain enterprises in the context of non-habitual coffee-drinking countries. Moreover, it provides case support for the operation and research of regional cultural consumption habits of international catering chain enterprises.