In order to improve the response speed of the shore-to-ship missile combat system, the structure composition and main functions of the shore-to-ship missile combat system are analyzed, and the network structure of the shore-to-ship missile combat system under the platform central warfare mode is established based on the complex network theory. The efficiency evaluation index system was constructed by using the performance index of complex network and the efficiency evaluation method was given. The network structure of the combat system was optimized through the network coordination of firepower layer, command layer, and pre-alarming detection layer. The results indicate that the network efficiency of the optimized combat system had been improved obviously.