The photoelectrochemical (PEC) water splitting is hampered by strong bonds of H2O molecules and low ionic conductivity of pure water. The photocatalysts dispersed in pure water can serve as a water activation agent, which provides an alternative pathway to overcome such limitations. Here we report that the light illuminated α-Fe2O3/Pt nanoparticles may produce a reservoir of reactive intermediates including H2O2, ·OH, OH(-) and H(+) capable of promoting the pure water reduction/oxidation half-reactions at cathode and highly photocatalytic-active TiO2/In2S3/AgInS2 photoanode, respectively. Remarkable photocurrent enhancement has been obtained with α-Fe2O3/Pt as water activation agent. The use of α-Fe2O3/Pt to promote the reactivity of pure water represents a new paradigm for reproducible hydrogen fuel provision by PEC water splitting, allowing efficient splitting of pure water without adding of corrosive chemicals or sacrificial agent.