Hematite (α‐Fe2O3) is a promising semiconductor for photoelectrochemical (PEC) water splitting, due to its abundance, low‐cost and excellent stability. However, the efficiency of α‐Fe2O3 photoelectrodes has been limited by its low hole mobility and fast electron‐hole recombination. Host‐guest architectures have emerged as a suitable design, which involves the use of a nanostructured collector for high solar absorption while maintaining an ultrathin absorber layer for better charge transport. In this study, a thin mesoporous SiO2 host template coated with a conductive thin layer of TiO2 was optimized to support the α‐Fe2O3 film. The α‐Fe2O3 thin layer was deposited by spray pyrolysis and then coated with a FeNiOOH co‐catalyst. A photocurrent improvement of ca. 85% over planar α‐Fe2O3 thin film reference was registered demonstrating the potential of this host‐guest approach.