The sustainable development of society will depend on the hydrogen economic, which should be based on the conversion of solar energy. Photoelectrochemical water splitting has become one of the most promising solar-to-hydrogen convert techniques. After near five-decade research, this technique has been in dilemma, mainly resulting from the lack of highly efficient and stable photoelectrodes. In recent years, the stability of photoelectrodes under operation seems to be resolve by the introduction of robust TiOx protective layer, which means that ways to enhancing the solar-to-hydrogen efficiency of photoelectrodes should be developed preferentially towards the realization of solar water splitting. Improvement of the charge transfer of the photoelectrodes would lead to the enhancement of the solar-to-hydrogen efficiency. Here, several main strategies for the optimization of charge transfer has been summarized. It is by the fabrication of micro/nano structure facilitating charge diffuse and drift, the introduction of dopants increasing the conductivity, the optimization of synthesis procedures minimizing the charge recombination defects, the construction of semiconductor junctions and the best choice of suitable substrates for the majority charge transport or the deposition of under layers that the photoelectrochemical performance of the given photoelectrode would be boosted.