By coupling α-Fe2O3 with a 3D graphene inverse opal (3D-GIO) conducting electrode, the short diffusion length of carriers and low absorption coefficient in α-Fe2O3 for photoelectrochemical applications were successfully addressed. GIO was directly grown on FTO substrate under low temperature conditions, removing the need for a graphene transfer process. α-Fe2O3 nanoparticles (NPs) were hydrothermally deposited on the surface of GIO, creating α-Fe2O3/GIO. The photocurrent density of α-Fe2O3/GIO in water splitting reactions reached 1.62 mA/cm2 at 1.5 V vs RHE, which is 1.4 times greater than that of optimized α-Fe2O3. The EIS and IPCE data confirm reduced electron-hole recombination and fast electron transfer processes due to the short distance between active materials and the conducting electrode in the α-Fe2O3/GIO system. Our result may pave the way for designing devices in advanced energy conversion applications as well as a high efficiency hematite-based PEC system.