Manufacturing service is the integration of manufacturing and service, and it is a manufacturing oriented service. For the plurality of external processing in manufacturing service among manufacturing enterprises, the manufacturing services business collaboration chain(BCC) has been established, and the collaboration chain was defined as multiple group. The five tuple chain model of business collaboration was established by using Petri net. However, the optimization of business collaboration chain was the NP Hard problem, then the greedy algorithm was adopted to optimize the BCC in which the Business Hours were selected as greedy factors. Through the example to verify the feasibility, the results of business collaboration chain optimization showed that the construction of business collaboration chain in manufacturing services and optimization of BCC could bring well decision making in business collaborative of manufacturing service, lay a solid foundation for the realization of intelligent manufacturing system in the end.