This paper addresses an energy-optimal attitude control strategy for space solar power satellites (SSPSs) during on-orbit energy transmission missions. The study focuses on a space solar power generation and energy transmission experimental satellite as the research object. First, the attitude dynamics of the satellite are modeled using the Lagrange method, and the satellite’s attitude control actuators, namely the single-gimbal control moment gyroscopes (SGCMGs), are also modeled to capture their dynamic behavior and constraints. Second, a PD controller based on quaternion and angular velocity error feedback is designed to achieve the desired attitude necessary for the energy transmission task. Subsequently, a hierarchical optimization approach is developed to obtain the energy-optimal attitude control strategy over one orbital period, considering multiple factors such as the satellite’s on-orbit energy consumption, the energy collection efficiency of the solar array in non-shadow regions, and the energy transmission efficiency between the satellite and the ground station. The optimization process is divided into two levels. In the first level, within the ground station’s visibility window, an energy balance analysis at different potential transmission moments is performed to determine the optimal transmission timing that maximizes the energy received by the ground station. In the second level, during the energy transmission phase, a cost function is formulated that incorporates pointing accuracy, pointing stability, and actuator energy consumption, and the controller parameters are globally optimized using the Adaptive Particle Swarm Optimization (APSO) algorithm. The simulation results demonstrate that the proposed hierarchical optimization method can significantly enhance the operational efficiency of on-orbit energy transmission, providing a practical engineering approach for the efficient on-orbit operation of future space solar power stations.