This work is developed to improve the current quality of e-commerce logistics services. From the perspective of multiple consumer psychology, based on e-commerce, consumer psychology, and other related theories, vegetable e-commerce B is selected as the research object. The commodity quality, accuracy, and timeliness of commodity distribution and other factors of e-commerce B are discussed through questionnaire survey. Then, according to customers’ opinions about “e-commerce B’s distribution and professional aspects that need to be improved,” the research is conducted. Finally, the direction of follow-up optimization is proposed from four different perspectives of multiple consumption psychology. The research results show that more than 89% of the surveyed customers believe that e-commerce B does a good job in terms of commodity quality, accuracy, and timeliness of commodity distribution, and has a high level of logistics service. However, 26.34% of customers hope that e-commerce B can strengthen the protection of personal privacy, 24.97% hope that the platform can add “delay insurance” for goods, and 39.54% hope that the logistics information of purchased goods can be updated in real time. Therefore, e-commerce B needs to be optimized and improved continuously in the future development. Therefore, research on the optimization of logistics service quality of e-commerce is performed under multiple consumption psychology, which provides certain help for the rapid development of subsequent e-commerce.