Traditional charging stations have a single function, which usually does not consider the construction of energy storage facilities, and it is difficult to promote the consumption of new energy. With the gradual increase in the number of new energy vehicles (NEVs), to give full play to the complementary advantages of source-load resources and provide safe, efficient, and economical energy supply services, this paper proposes the optimal operation strategy of a PV-charging-hydrogenation composite energy station (CES) that considers demand response (DR). Firstly, the operation mode of the CES is analyzed, and the CES model, including a photovoltaic power generation system, fuel cell, hydrogen production, hydrogen storage, hydrogenation, and charging, is established. The purpose is to provide energy supply services for electric vehicles (EVs) and hydrogen fuel cell vehicles (HFCVs) at the same time. Secondly, according to the travel law of EVs and HFCVs, the distribution of charging demand and hydrogenation demand at different periods of the day is simulated by the Monte Carlo method. On this basis, the following two demand response models are established: charging load demand response based on the price elasticity matrix and interruptible load demand response based on incentives. Finally, a multi-objective optimal operation model considering DR is proposed to minimize the comprehensive operating cost and load fluctuation of CES, and the maximum–minimum method and analytic hierarchy process (AHP) are used to transform this into a linearly weighted single-objective function, which is solved via an improved moth–flame optimization algorithm (IMFO). Through the simulation examples, operation results in four different scenarios are obtained. Compared with a situation not considering DR, the operation strategy proposed in this paper can reduce the comprehensive operation cost of CES by CNY 1051.5 and reduce the load fluctuation by 17.8%, which verifies the effectiveness of the proposed model. In addition, the impact of solar radiation and energy recharge demand changes on operations was also studied, and the resulting data show that CES operations were more sensitive to energy recharge demand changes.