Major advantages can be achieved for service improvement in modern logistics through effective collaborations. As a result, many logistics operational processes have developed into collaborative logistics chains involving different organizations. Organizational behaviors have a strong impact on the success of collaborations. However, it remains a challenging problem to reveal the real organizational behaviors in the collaborative logistics chains in a dynamic environment. This paper investigates the organizational behaviors in collaborative logistics chains from a process perspective using a synergy of process mining and social network analysis techniques. A method for mining organizational behaviors is presented, including process event log collection, work delivery flow discovery, and organization structure mining. An empirical study is conducted in an important Chinese port. Insights are obtained in terms of the working delivery patterns and organizational structures in the collaborative logistics chain. Recommendations to enhance the collaborations are given.