Poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonate) (PEDOT: PSS) and polyethylene oxide (PEO) (or polyvinyl alcohol (PVA)) blended electrospun nanofibers were prepared in the presence of dimethyl sulfoxide (DMSO) and ethylene glycol (EG). The effects of added solvents (DMSO and EG) and blended polymers (PEO and PVA) on electrical conductivity and current-voltage (I-V) response were investigated. Electrical conductivity was dependent on both the additional solvent and blended polymers. PEDOT: PSS/PEO blended nanofibers showed a much higher electrical conductivity than PEDOT: PSS/PVA. EG blended PEDOT: PSS/PEO blended nanofibers showed much higher electrical conductivity than DMSO. The PEDOT: PSS/PEO/EG blended nanofibers web showed the highest value in I-V response.