To realize highly efficient solar-thermo-electric energy conversion for clean electricity power generation, we have developed a new type of unidirectionally structured magnetic phase-change composite comprising a carbonized polyimide (C-PI)/Kevlar nanofiber (KNF) complex aerogel as a 3D carbon skeleton porous supporting material, CoFe2O4 nanoparticles as a magnetic additive, polyethylene glycol (PEG) as a phase-change material, and polypyrrole as a photothermal absorption coating layer. The as-fabricated C-PI/KNF complex aerogel exhibits a unidirectional microstructure, high porosity, robust skeleton frame, ultralight weight, and high thermal conductance. Featured with such unique structure and characteristics, the complex aerogel can offer an effective heat and electron transfer method to ensure highly efficient solar-thermal conversion and photothermal energy storage of the developed composite. The developed composite exhibits a high latent heat capacity of over 150 J g-1, outstanding shape stability along with a low leakage of 0.2 wt %, good thermal cycling stability, and high photothermal conversion efficiency of 84.8%. Based on the Seebeck effect, a solar thermoelectric generation system (STEGS) was constructed with the hot side coupled with the developed composite and the cold side immersed in air and ice water. Under 2.0 kW m-2 solar irradiation, the developed STEGS in ice water obtained maximum output voltage and current of 259.7 mV and 27.1 mA, respectively, which are significantly higher than those in air. The output power of the developed STEGS in an ice water environment is 50.6% higher than that in air under 4.0 kW m-2 solar irradiation. More importantly, the developed STEGS in ice water continuously generated output voltage and current for about 810 s without solar irradiation thanks to the latent heat release by the PEG component within the developed composite. In addition, the introduction of magnetic CoFe2O4 can accelerate solar-thermal conversion through periodic electron motion by the Néel relaxation or Brownian relaxation. This resulted in an increase in the maximum output voltage and current by 13.7 and 11.5%, respectively, under an alternating magnetic field as a result of the magnetism-accelerated solar-thermo-electric conversion. This study offers an innovative approach for developing PCM-based advanced functional materials for solar energy utilization in clean and sustainable electricity generation.