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In order to achieve the carbon peaking and carbon neutrality goals, one of China’s choices is to establish distributed photovoltaic power station (DPPS). the site combination optimization is important for DPPS. If the government’s opinions are not considered in the decision-making, the DPPS project will be aborted. Because the decision-making objectives of the enterprise and the local government are inconsistent and cannot compensate each other, it is necessary to build the decision index systems based on the respective decision-making objectives of enterprises and governments. The DPPS site combination optimization is the multi-objective programming (MOP) problem, but the MOP model is difficult to operate in the dual perspective environment, because the complexity of decision index system and the data type diversity and uncertainty of decision information. Therefore, the innovations of this paper are as follows: ① the DPPS site selection decision index system is established from the dual perspective of enterprises and governments, so as to ensure the interest demands of local governments and lay a foundation for win–win; ② The proposed site combination optimization model has better inclusiveness to the types of decision data with the help of interval-valued intuitionistic fuzzy number (IVIFN), so as to reduce the impacts of information loss and uncertainty; ③ and more importantly, the proposed model can solve the DPPS site combination optimization problem in the environment of complex decision index system with the help of IVIFN–TOPSIS method. The proposed decision index system and model form the site combination optimization framework, and its effectiveness is verified by a case study. This framework can provide a reasonable basis for cooperation negotiations, thereby promoting the further development of DPPS and providing the necessary reference for other types of new energy power stations.