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The development of photovoltaic industry can effectively alleviate the energy crisis and environmental pollution. The deployment of photovoltaic power stations along the high-speed railway is a new mode combining photovoltaic new energy with infrastructure. This paper constructs a comprehensive decision-making framework for the site selection of PV power station along high-speed railway combining the subjective method and the objective method. A scientific and reasonable evaluation index system comprehensively considering multiple factors is constructed in this framework. Analytic hierarchy process and Entropy weight method are combined to determine the weight of every index, which combines the expert knowledge and data information effectively, relatively reducing systematic error and random error. Grey relational analysis is used to choose scheme among several alternatives, which greatly deal with the strong grey correlations among indexes. The framework established in this paper is used to select PV power stations along the Beijing-Shanghai high-speed railway, which also verifies the effectiveness of the framework.