This paper aims to discuss the relational risks in supply chain and its governance mechanism, including formal and informal control mechanisms and trust development mechanisms, to provide a new idea of relational risks management in supply chain domains and then enhance the interests of all involved parties. The governance efficiency of relational risks in supply chain can be improved by control mechanisms associated with trust development mechanisms, and both of which are dynamic complementary. Initial trust among partners impacts the inter-organizational relational performance and the choice of control mechanisms, at the same time, the outcomes of relationship and the development or destruction of trust mechanisms are affected by control modes.