The open-circuit voltage of CH3NH3PbI3 based photovoltaics was enhanced from 0.77 V to 0.9V, which resulted in an improvement of the average power conversion efficiency from 5.63% to 11.74% achieved by tuning the work function of the poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) hole transport layer. The higher work function of the PEDOT:PSS (1:20wt%) thin film, as compared to the PEDOT:PSS (1:6wt%) and PEDOT:PSS (1:2.5wt%) thin films, was observed using photoelectron spectrometer. The carrier density of PEDOT was obtained by analyzing the transmittance spectrum of PEDOT:PSS/glass with the transfer matrix method. The Drude model can be used to explain the increased work function of the PEDOT:PSS thin film obtained by decreasing the ratio of PEDOT to PSS. The increased carrier density of the PEDOT in PEDOT:PSS thin films originated from conformational changes in the PEDOT chains as confirmed by Raman scattering spectroscopy.