Obtaining small, fast, and energy-efficient spintronic devices requires a new way of manipulating spin states in an effective manner. Here, a prototype photovoltaic spintronic device with a p-n junction Si wafer is proposed which generates photo-induced electrons and changes the ferromagnetism by interfacial charge doping. A ferromagnetic resonance field change of 48.965 mT and 11.306 mT is achieved in Co and CoFeB thin films under sunlight illumination, respectively. The transient reflection (TR) analysis and the first principles calculation reveal the photovoltaic electrons that are doped into the magnetic layer and alter its Fermi level, correspondingly. This finding provides a new method of magnetism modulation and demonstrates a solar-driven spintronic device with abundant energy supply, which may further expand the landscape of spintronics research.