Express parcel delivery has increased significantly in recent years because of changes in technology and consumer habits, as has the number of express parcel delivery companies and the competitiveness among them. For an express parcel business to be sustainable, it must succeed in increasing customer perceived value (CPV). This study aims to investigate the business-to-business (B2B) performance between companies and their main express parcel service provider. The main objective was to analyze the impact of CPV on both the intention to repurchase services and the intention to recommend such services in the business-to-business (B2B) express parcel delivery sector. This study develops a research model that is analyzed in the express parcel sector in Spain using the variance-based structural equation technique, partial least squares (PLS-SEM), for data analysis. The findings reveal that with express parcel services in the B2B sector, perceived value was positively associated with the customer’s perceived satisfaction and trust, which in turn enhances the intention to repurchase and stimulates advocacy. In a market as competitive as the express parcel market in the B2B environment, customer perceived value is a critical factor in ensuring company sustainability.