We have successfully functionalized multiwalled carbon nanotubes (MWCNTs) using nitrene approach employing the two aryl azides as a precursor for nitrene generation. The dispersion of functionalized MWCNTs has been enhanced in various organic solvents. These functionalized MWCNTs have been successfully doped in various concentrations in the bulk heterojunction (BHJ) organic photovoltaic (OPV) cells with a poly (3-hexyl thiophene) (P3HT) and 6,6-phenyl-C61-butyric acid methyl ester (PCBM) photoactive blended layer. The incorporation of MWCNTs with aryl functional groups, in active the layer, results in enhanced performance with respect to a reference cell. The maximum power conversion efficiency of 1.86% is achieved with adduct I while in the case of adduct II it gets double to 2.0% in comparison with a reference cell. This improvement in the device performance is attributed to enhanced exciton dissociation and improved charge transport properties due to the formation of a nanotube percolation network in the photoactive composite layer.