The nickel phthalocyanine (NiPc) thin film has been explored for magneto-conductance and optoelectrical properties. The surface morphology and the opto-electrical properties of thin films of NiPc have been observed as a good candidate for the applications in polymer solar cells. The AFM images show an almost continuous surface over the studied area. The spin interaction, the disordering of the spins part, and their suitable models have been discussed by the magneto-conductance properties of the thin films. The relaxation time of carriers and traps filling phenomena with applied bias are discussed by the impedance spectroscopy. The thin films of NiPc have been introduced as a hole interface buffer layer in the standard structure of P3HT: PCBM solar cells. The power conversion efficiency (PCE) of the optimized solar cell with NiPc is ∼3.17% and the fill factor (FF) is ∼69%., these device parameters are higher (PCE increased by ∼65% and FF by ∼39%) as compared to the organic solar cells fabricated without NiPc thin films in the same batch. The improved performance of organic solar cells attributed due to lowering the series and shunt resistance.