In order to assess the influence of combat organizational structure on operational effectiveness dynamically, the network characteristic of combat organizational structure on condition of information was analyzed by using complex network theory. Considering the heterogeneity of combat organizational entity and organizational structure relation, a multi-dimensions weighted operational network model was firstly constructed, and then the characteristic value of cooperative gain, which depicts the performance of operational network, was defined. Under this, to enhance operational effectiveness, two dynamic evolution models of operational network, which are random evolution model and preferred evolution model, were designed, and the internal relation and influence law between operational network dynamic evolution and operational effectiveness was analyzed by using the models along with the characteristic values of cooperative gain. Finally, simulation results show the feasibility of the proposed method, which can be used to provide theoretical basis for designing and optimizing combat organizational structure.