The effect of incorporation of ethylene glycol (EG) into poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) on electron phonon coupling and conductivity is investigated. It is shown that the carrier density (NC) increases significantly and the carrier mobility (μ) increases slightly at 300 K. The increased intensity of the Raman spectrum between 1400 and 1450 cm−1, following EG treatment (that is, the quinoid-dominated structures of the PEDOT chain), leads to an increase in the number of polarons (bipolarons), which leads to an increase in NC. In addition, μ in PEDOT:PSS samples with or without EG addition exhibits a strong temperature dependence, which demonstrates the dominance of tunneling (hopping) at low (high) temperatures. The high conductivity of PEDOT:PSS samples with the addition of EG is attributed to the combined effect of the modification of the electron-phonon coupling and the increase in NC (μ).