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 Cd0.55Zn0.45O due to its favorable positions of the band extrema to the water splitting potentials and a band gap similar to 2.0 eV. The Grading layer (Sub-G) was composed of CdxZn1-xO 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 electron Barrier 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 Ni0.4Cd0.6O film with E-g similar to 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% 1 M K2HPO4 and 13% 1 M Na2SO3 (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 similar to 0.05 mA/cm(2) to similar to 20 mA/cm(2) at +1.2 V for visible light. The observed Incident Photon-to-Current Efficiency (IPCE) was about 50% measured at a photon energy of 3 eV. (C) 2016 Elsevier B.V. All rights reserved.