Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), a conducting polymer, has been receiving a great deal of attention for next generation optoelectronic organic devices. In this report, we discuss the effect of additives along with the thickness of PEDOT:PSS layers on the power conversion efficiency of organic solar cell devices. PEDOT:PSS films treated with high boiling point solvents of dimethyl sulfoxide (DMSO) and ethylene glycol (EG) show a significant enhancement in electrical conductivity without compromising flexibility or optical transparency. The conductivity increased from 0.5 to 517 and 724 S/cm after once and thrice treatment with 4 vol. % EG, respectively. The as-prepared and additives-treated PEDOT:PSS films deposited on glass substrates have been investigated by optical spectroscopy, micro-Raman spectroscopy and atomic force microscopy (AFM). The results indicate that structural and morphological changes were induced by the additive processes. By using DMSO and EG treated PEDOT:PSS as a hole transport layer, organic solar cells with a Poly[[9-(1-octylnonyl)-9H-carbazole-2,7-diyl]-2,5-thiophenediyl-2,1,3-benzothiadiazole-4,7-diyl-2,5-thiophenediyl]:[6,6]-phenyl-C71-butyric acid methyl esters (PCDTBT:PC71BM) bulk heterojunction have been fabricated on indium-tin-oxide (ITO) coated glass substrates. The high power conversion efficiency (PCE) of 5.17%, and 5.69%, were observed for PEDOT:PSS hole transport layers treated with DMSO and EG respectively, even though the devices were prepared in air atmosphere. © 2013 The Korean Institute of Metals and Materials and Springer Science+Business Media Dordrecht.