The optical and electrical properties of PVA/PVP were manipulated by optimizing the blend ratio between those polymers. The (40/60) wt.% of PVA/PVP achieved the lowest energy gap and the highest electrical conductivity. After that, the optical and electrical properties of blend films were engineered using Ni(OAc)2 for enhanced optoelectronic properties. The doping impact on the semicrystalline and molecular structures of the prepared blend was investigated. The optical properties of the doped blend films were examined using optical transmission and absorption spectra measurements. The nonlinear optical parameters such as nonlinear refractive index and third-order optical susceptibility were estimated. The prepared films showed a pronounced laser cut-off performance. The electrical properties of the fabricated films showed a tunable behavior with the variation of doping level. The engineered doped polymer blend films exhibited good sensitivity to visible light with promising values of responsivity and specific detectivity ∼5.89 mA/W, and 4.31 × 109 Jones, respectively.