With the development of information communication and satellite positioning, crowd logistics has gradually emerged as a popular urban distribution mode for logistics enterprises. Trust and synergy between the crowd workers and the crowd logistics enterprises have become key issues in urban logistics development. Based on commitment-trust theory and logistics synergy, this paper developed a theoretical model exploring ability trust, goodwill trust, logistics synergy, and crowd logistics operational performance. We used SmartPLS software to analyze the questionnaire survey from 50 senior managers in crowd logistics enterprises. The results show that ability trust has a significant positive impact on logistics synergy and operational performance. Logistics synergy was also found to increase the operational performance of crowd logistics enterprises and plays a mediating role in the impact of ability trust and goodwill trust on operational performance. We recommend that logistics enterprises evaluate their crowd workers’ service abilities, promote trust relationships with them, strengthen the construction of crowd logistics mechanisms, and invest in crowd worker training and development.