E-commerce has provided companies almost in every industry to introduce new ways of serving their customers. As with any other markets, physical distribution service (PDS) industry experienced an upswing in the adoption of e-services. This study has attempted to find the limitations and enhancing factors of e-commerce usage, the determinants of e-service and PDS quality, and their underlying relationships in business-to-business physical distribution services, particularly in a pharmaceutical wholesale context. This study provides valuable insights for the multi-channel non-retail PDS industries in terms of the reasons underlying customers’ channel preferences and the aspects vital for achieving total quality in their services and respective customer satisfaction. Given the increasing role played by technology in shaping business relationships and transactions in this industry, managers need to pay attention to the level of quality associated to their e-services, because just as overall satisfaction with services, e-satisfaction from e-services is also a strong determinant of customers’ future relationships with the distributor.