Bulk heterojunction (BHJ) solar cells have made great progress over the past decade and consequently are now attracting extensive academic and commercial interest because of their potential advantages: lightweight, flexible, low cost, and high-throughput production. Polymer conductivity is a key factor for improving the performance of electronic and photonic devices. Poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) is promising for use as a next-generation transparent electrode of optoelectronic devices. In this research, we compare the effect of nanomorphology on conductivity, and power conversion efficiency of polymer organic solar cells prepared by the spin- and spray-coating methods. To improve the conductivity of spray-deposited PEDOT:PSS, we modified the PEDOT:PSS films by simple UV irradiation and by UV irradiation with treatment using various solvents such as methanol, ethanol, acetone, acetonitrile, hydrochloric acid, and sulfuric acid to form a hole transport layer (HTL). The active layer of PTB7:PC70BM is spray-coated on top of the PEDOT:PSS layer. The films were examined by optical spectroscopy, micro- Raman spectroscopy, and conductivity measurements. The surface morphology of the deposited films was examined by atomic force microscopy (AFM). The current density-voltage (J-V) characteristics were measured under illumination with simulated solar light at 100mW/cm2 (AM 1.5G) using an oriel 1000W solar simulator. The obtained results are expected to have a considerable impact and suggest a bright future for organic polymer solar cells. © 2014 The Japan Society of Applied Physics.