Films of poly(3,4-ethylenedioxythiophene)–polystyrenesulfonic acid (PEDOT–PSS), prepared by coating the aqueous PEDOT–PSS dispersion and by coating a mixture of the PEDOT–PSS dispersion and different solvents, have been studied using four-point probe conductivity measurements, atomic force microscopy and photoelectron spectroscopy. The electrical conductivity of thin films of the second type (further on called PEDOT–PSS–solvents) was increased by a factor of about 600 as compared to films of the first type (further on called PEDOT–PSS–pristine). Morphological and physical changes occur in the polymer film due to the presence of the solvent mixture, the most striking being that the ratio of PEDOT-to-PSS in the surface region of the films is increased by a factor of 2–3. This increase of PEDOT at the surface indicates that the thickness of the insulating PSS ‘shell’ that surrounds the conducting PEDOT–PSS grains is reduced. The (partial) reduction of the excess PSS layer that surrounds the conducting PEDOT–PSS grains is proposed to lead to an increased and improved connectivity between such grains in the film and hence a higher conductivity. When PEDOT–PSS–solvents receives a post-coating heat treatment, the increased PEDOT-to-PSS ratio at the surface is maintained or even slightly improved, as is the increase in electrical conductivity, even though spectroscopy show that the solvent molecules are removed. This suggests that screening or doping by the solvents throughout the film are not likely to be the key mechanisms for the improved conductivity and supports our proposed mechanism of improved conductivity through improved connectivity between the conducting grains.