Conductive copolymer poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) has been proposed as an alternative to transparent conductive oxides because of its flexibility, transparency, and low-cost production. Four different secondary dopants, namely N,N-dimethylformamide, ethylene glycol, sorbitol, and dimethyl sulfoxide, have been used to improve the conductivity. The relation between the structure changes and conductivity enhancement is studied in detail. Atomic force microscopy study of the thin film surface reveals the phase separation of PEDOT and PSS. We demonstrate that secondary doping induces the phase separation as well as the conductivity enhancement. (C) 2016 Elsevier B.V. All rights reserved.