Stable, conductive films of poly(3-alkylthiophenes) (P3ATs) can be obtained from a single chloroform based solution containing polymer, oxidant (silver triflate), and an oxidantcoordinating ligand (pyridine). Casting of this solution, followed by evaporation of the ligand, results in an electronically conductive film which is more stable and, notably, in the case of thick films, is free of the cracking which often results from swelling of the films during the doping process. This technique, coined solvato-controlled oxidative doping, results in films possessing enhanced stability compared to those oxidized by conventional dopants such as ferric chloride. Also, these silver-containing films are much more stable than those electrochemically doped with the triflate anion. Thus, the presence of metallic silver in the doped film has a profound effect on the stability of the conducting form.