Wet-processable and highly conductive polymers are promising candidates for key materials in organic electronics. Poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) is commercially available as a water dispersion of colloidal particles but has some technical issues with PSS. Here, we developed a novel fully soluble self-doped PEDOT (S-PEDOT) with an electrical conductivity as high as 1089 S cm−1without additives (solvent effect). Our results indicate that the molecular weight of S-PEDOT is the critical parameter for increasing the number of nanocrystals, corresponding to the S-PEDOT crystallites evaluated by x-ray diffraction and conductive atomic force microscopic analyses as having high electrical conductivity, which reduced both the average distance between adjacent nanocrystals and the activation energy for the hopping of charge carriers, leading to the highest bulk conductivity.