The present work is a detailed study of the optical, morphological and electrical properties of poly (3,4-ethylenedioxythiophene):poly(styrenesulfonate), PEDOT:PSS, films doped with ethylene glycol (EG) and multi-walled carbon nanotubes (MWCNT). The conductivity of PEDOT:PSS films doped with EG and MWCNT is higher than pristine PEDOT:PSS film. The optical transparency of PEDOT:PSS film decreases insignificantly after addition of MWCNT and EG. The films were further studied using atomic force microscopy, x-ray diffraction, Raman spectroscopy and Kelvin probe work function measurement, after which films of PEDOT:PSS with EG and MWCNT were optimized for the fabrication of solar cells. The optimized film was used as a hole extracting layer in a typical ITO/PEDOT:PSS/ P3HT:PCBM/Al solar cell. The suitable concentration for an optimized film was found to be 4% MWCNT and 1:4 ratio of EG to PEDOT:PSS. The performance of the device with doped PEDOT:PSS was found to improve in terms of short circuit current density (J SC ) and efficiency (η). The solar cell with a doped PEDOT:PSS layer showed higher J SC and η due to the increase in the interchains among PEDOT chains along with the introduction of MWCNT channels in PEDOT:PSS matrix. The degradation behavior of the cells was studied and it was found that both pristine and doped PEDOT:PSS cells showed similar trends of degradation. The performance degradation with time was also studied under variable environmental conditions, which showed different aging rates for the two devices.