Crystalline ZnTeO thin films are promising materials for next generation photovoltaics. However, their structural stability and optical nonlinearity potential in bulk form have not been reported. Here, structural, electronic and optical properties of ZnTeO composites have been thoroughly studied using genetic algorithm and density functional theory (DFT). Energetically, mechanically and dynamically stable O-rich phases, namely Zn2Te2O6 and ZnTeO4, were obtained. Ground-state properties such as lattice constants and simulated XRD were analyzed and compared to the experimental literature wherever possible. With a G 0 W 0 corrected band gap, these semiconducting phases display several desirable features, namely, Jahn-Teller distorted cations, hardness and shear anisotropy-induced optical nonlinearity that increase monotonically as O concentration elevates. Such trends appear to be consistent with that seen in the experimental study of ZnTeO thin film. It is observed that Zn-d, Te-p and O-p states have immense influence towards the electronic properties of these structures. Both phases exhibit steep elevation of absorption throughout the ultraviolet (UV) range, hitting peak value of ~5.0 × 105 cm-1. Of particular interest, the non-centrosymmetric ZnTeO4 has second harmonic generation coefficients (9.84 pm V-1 and 2.33 pm V-1 at static limit) greater than borates crystal and large birefringence that exceeds 0.08 in deep UV region, thus highlighting its potential pedigree as new optical materials in UV range.