Herein, a route to produce highly electrically conductive doped hydroxymethyl functionalized poly(3,4-ethylenedioxythiophene) (PEDOT) films, termed PEDOT(OH) with metal-like charge transport properties using a fully solution processable precursor polymer is reported. Further, this is achieved via an ester-functionalized PEDOT derivative PEDOT(EHE) that is soluble in a range of solvents with excellent film-forming ability. PEDOT(EHE) demonstrates moderate electrical conductivities of 20–60 S cm-1 and hopping-like (i.e., thermally activated) transport when doped with ferric tosylate (FeTos3). Upon basic hydrolysis of PEDOT(EHE) films, the electrically insulative side chains are cleaved and washed from the polymer film, leaving a densified film of PEDOT(OH). These films, when optimally doped, reach electrical conductivities of ≈1200 S cm-1 and demonstrate metal-like (i.e., thermally deactivated and band-like) transport properties and high stability at comparable doping levels.