We explored the photophysics of an all polymeric solar system based on the combination of the wide bandgap polymers poly(3-hexylthiophene) (P3HT) as donor and low bandgap polymer poly{[N,N-9-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,59-(2,29-bithiophene)} (P(NDI2OD-T2)) as an acceptor blend active layer in 2-methyl anisole using airbrush spray coating method. Polyethyleneimine ethoxylated (PEIE) is used as the surface modifier and SnO2 as an anode, to minimize the chemical damage of the transparent conducting electrode. The molecular aggregations were investigated by means of absorbance, photoluminescence measurements and atomic force microscopy. The current density–voltage characteristics were examined using an Oriel 1000W solar simulator under the illumination condition through the simulated solar light with 100 mW cm−2 (AM 1.5G). The power conversion efficiency (PCE) of about 5.6% is been reported for the photovoltaic device and this outcome indicates that these spray coating method can be a feasible technique when compared with other high-cost vacuum deposition techniques for mass production and low-cost roll to roll based fabrication. © 2017 Elsevier Ltd