The quality of logistics service is a major criterion to measure the logistics industry. This article explores the correlation analysis between the factors affecting the quality of logistics service and the express business volume. Using reliability, economy, timeliness, flexibility, information availability, recommendation and praise as latent variables, the structural equation model of logistics service quality-express business volume is constructed. Five dimensions of logistics service quality and the correlation between customer satisfaction and express business volume are defined, and a distribution survey scale is designed. The entropy weight method is used to process the data, and the correlation and regression analysis are carried out on the processed survey data. The results show that flexibility and information availability are the key factors affecting the volume of express delivery business, thus providing reasonable suggestions for China’s logistics enterprises to improve service quality and increase the volume of express delivery business.