Phosphoric acid (PA)–doped polybenzimidazole (PBI) proton exchange membranes have received attention because of their good mechanical properties, moderate gas permeability, and superior proton conductivity under high temperature operation. Among PBI-based film membranes, nanofibrous membranes withstand to higher strain because of strongly oriented polymer chains while exhibiting higher specific surface area with increased number of proton-conducting sites. In this study, PBI electrospun nanofibers were produced and doped with PA to operate as high temperature proton exchange membrane, while changes in proton conductivity and morphologies were monitored. Proton conductive PBI nanofiber membranes by using the process parameters of 15 kV and 100 μL/h at 15 wt% PBI/dimethylacetamide polymer concentration were prepared by varying PA doping time as 24, 48, 72, and 96 hours. The morphological changes associated with PA doping addressed that acid doping significantly caused swelling and 2-fold increase in mean fiber diameter. Tensile strength of the membranes is found to be increased by doping level, whereas the strain at break (15%) decreased because of the brittle nature of H-bond network. 72 hour doped PBI membranes demonstrated highest proton conductivity whereas the decrease on conductivity for 96-hour doped PBI membranes, which could be attributed to the morphological changes due to H-bond network and acid leaking, was noted. Overall, the results suggested that of 72-hour doped PBI membranes with proton conductivity of 123 mS/cm could be a potential candidate for proton exchange membrane fuel cell.