We report on the development of high performance triple and quadruple junction solar cells made of amorphous (a-Si:H) and microcrystalline silicon (μc-Si:H) for the application as photocathodes in integrated photovoltaic-electrosynthetic devices for solar water splitting. We show that the electronic properties of the individual sub cells can be adjusted such that the photovoltages of multijunction devices cover a wide range of photovoltages from 2.0 V up to 2.8 V with photovoltaic efficiencies of 13.6 % for triple and 13.2 % for quadruple cells. The ability to provide self-contained solar water splitting is demonstrated in a PV-biased electrosynthetic (PV-EC) cell. With the developed triple junction photocathode in the a-Si:H/a-Si:H/μc-Si:H configuration we achieved an operation photocurrent density of 7.7 mA/cm2 at 0 V applied bias using a Ag/Pt layer stack as photocathode/electrolyte contact and ruthenium oxide as counter electrode. Assuming a faradic efficiency of 100 %, this corresponds to a solar-to-hydrogen efficiency of 9.5 %. The quadruple junction device provides enough excess voltage to substitute precious metal catalyst, such as Pt by more earth-abundant materials, such as Ni without impairing the solar-to-hydrogen efficiency.