Below we present semiempirical modeling of conceptually new three-sublayer photoanode, composed of Absorber, Grading and Barrier sublayers, for highly efficient photoelectrochemical water dissociation. The modeling resulted into Absorber (Sub-A) made of Cd 0.55 Zn 0.45 O due to its favorable positions of the band extrema to the water splitting potentials and a band gap ~2.0 eV. The Grading layer (Sub-G) was composed of Cd x Zn 1-x O with a gradual decrease of x across the profile, changing from 0.2 to 0.55, aiming to photon absorption from 2.0 to 3.0 eV. At the same time, Sub-G furnishes the profile with an implanted electrical field that improves the hole-transport. The electronBarrier layer (Sub-B) deposited above the Sub-A, was engineered to provide 1 eV high barrier in the conduction band. It comprised of a 50 nm thick Ni 0.4 Cd 0.6 O film with E g~3 .0 eV with a valence band aligned to the one of the Sub-A, providing a barrier-free hole-flow. In this paper, we provide evidence that the proposed three-sublayer concept clearly represents a new paradigm for an improved efficiency for photocatalytic water dissociation. The highest photocatalytic activity of the optimized profile was achieved with an optimized electrolyte: 87% 1M K 2 HPO 4 and 13% 1M Na 2 SO 3 (known to act as a hole scavenger or sacrificial agent) at pH=10. A noteworthy feature of this study is that under optimized profile parameters and customized electrolyte conditions the photocurrent yields increased from ~0.05 mA/cm 2 to ~20 mA/cm 2 at +1.2 V for visible light. The observed Incident Photon-to-Current Efficiency (IPCE) was about 50% at a photon energy of 3 eV.