The invention relates to a multi-quantum well photovoltaic battery based on a nanometer graphite electron transmission layer, and a preparation method thereof. The battery comprises a front electrode, an anti-reflection layer, N-type silicon, P-type silicon and a back electrode, wherein a composite layer composed of graphite and semiconductor quantum dots is arranged between the anti-reflection layer and the N-type silicon. Compared to the prior art, the method is characterized in such a way that a sol method is employed, first of all, a semiconductor quantum dot colloid is prepared; under the effect of a surfactant, the graphite is uniformly dispersed to the colloid, and then, by taking the graphite as a crystal growth liquid, a uniform an ordered electron transmission layer and a semiconductor quantum dot layer are grown on the surface of a crystal silicon chip in a deposition mode. According to the invention, by use of a quantum dot impact ionization effect and a namometer effect and excellent electron separate transmission performance of nanometer graphite, the minority carrier life and the quantum efficiency of the photovoltaic battery are improved, and the nanometer graphite can improve separation and collection of electrons by the silicon solar battery, improves photoelectric currents and accordingly improve the conversion efficiency of the silicon solar battery.