Multi-crystalline silicon (mc-Si) solar cells with passivated emitter and rear cell (PERC) structure were successfully fabricated on an industrial production line, and the effects of PERC structure on the power conversion performance of the solar cells were studied. The results indicate that, the PERC mc-Si solar cells exhibit an enhanced short-circuit current and open-circuit voltage, resulting in high power conversion efficiency of up to 20.14%. The enhanced optoelectronic conversion can be attributed to the reduced parasitic absorption loss of long wavelength photons and reduced recombination of charge carriers on the rear surface of PERC mc-Si solar cells. The PERC structure can improve the conversion efficiency of mc-Si solar cells, and can be compatible with traditional process, thus it can be regarded as an optimal cell structure.