Cu and Y co-doped hematite (α-Fe 2 O 3 ) nanostructured photoanodes with excellent optical properties were synthesized for photoelectrochemical water splitting (PWS) applications. The effects of the dopants on the crystal structure, morphology, and optical and chemical properties of the Fe 2 O 3 photoanodes were investigated. Structural and chemical analyses confirmed the substitution of Cu and Y ions into the Fe 2 O 3 nanostructures. With an increase in the Y dopant concentration, the bandgap of the photoanodes decreased from ~1.85 to ~1.35 eV. The dopants acted as charge contributors and enhanced the electron-hole densities of the photoanodes. The co-doped Fe 2 O 3 photoanodes showed higher photocurrents and hence higher incident light absorption capacities than did the undoped and Cu-doped samples. The α-Fe 2 O 3 photoelectrode co-doped with 0.3 mol% Y and 0.1% Cu showed the highest photocurrent density of ~0.44 mA/cm 2 , which is ~41 times of that of the undoped Fe 2 O 3 (0.01 mA/cm 2 ) photoanode and ~ 7 times of that of the 0.1 mol% Cu-doped α-Fe 2 O 3 photoanode. Furthermore, the Cu-doped photoanode showed a very low photocurrent density of 0.06 mA/cm 2 , which is only ~6 times of that of the undoped α-Fe 2 O 3 photoanode. The high photocurrents of the co-doped photoanodes can be attributed to their high electron donor densities and low electron-hole recombination rates. • Cu 2+ and Y 3+ co-doped Fe 2 O 3 nanostructures prepared by simple hydrothermal method • Dopant effect on morphology has been studied • The charge carrier generation and kinetics of the photoanodes were investigated • Optimized photoanode shows the maximum photocurrent density of ~0.45 mAcm −2