Various noble metal-free electrocatalysts have been explored to enhance the overall water splitting efficiency. Ni-based compounds have attracted substantial attention for achieving efficient oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) catalysts. Here, we show superior electrocatalysts based on NiFe alloy electroformed by a roll-to-roll process. NiFe (oxy)hydroxide synthesized by an anodization method for the OER catalyst shows an overpotential of 250 mV at 10 mA cm(-2), which is dramatically smaller than that of bare NiFe alloy with an over-potential of 380 mV at 10 mA cm(-2). Electrodeposited NiMo films for the HER catalyst also exhibit a small over-potential of 100 mV at 10 mA cm(-2) compared with that of bare NiFe alloy (550 mV at 10 mA cm(-2)). A combined spectroscopic and electrochemical analysis reveals a clear relationship between the surface chemistry of NiFe (oxy)hydroxide and the water splitting properties. These outstanding fully solution-processed catalysts facilitate superb overall water splitting properties due to enlarged active surfaces and highly active catalytic properties. We combined a solution-processed monolithic perovskite/Si tandem solar cell with MAPb(I0.85Br0.15)(3) for the direct conversion of solar energy into hydrogen energy, leading to the high solar-to-hydrogen efficiency of 17.52%. Based on the cost-effective solution processes, our photovoltaic-electrocatalysis (PV-EC) system has advantages over latest high-performance solar water splitting systems.