Thin film silicon tandem junction solar cells based on amorphous silicon (a-Si:H) and microcrystalline silicon (µc-Si:H) were developed with focus on high open-circuit voltages for the application as photocathodes in integrated photoelectrochemical cells for water electrolysis. By adjusting various parameters in the plasma enhanced chemical vapor deposition process of the individual µc-Si:H single junction solar cells, we showed that a-Si:H/µc-Si:H tandem junction solar cells exhibit open-circuit voltage over 1.5 V with solar energy conversion efficiency of 11% at a total silicon layer thickness below 1 µm. Our approach included thickness reduction, controlled SiH4 profiling, and incorporation of intrinsic interface buffer layers. The applicability of the tandem devices as photocathodes was evaluated in a photoelectrochemical cell. The a-Si:H/µc-Si:H based photocathodes exhibit a photocurrent onset potential of 1.3 V versus RHE and a short-circuit photocurrent of 10.0 mA/cm2. The presented approach may provide an efficient and low-cost pathway to solar hydrogen production.