We have developed a new 1,4-phenylenediamine polymer with suitable properties for the anode buffer layer of organic devices. The anode buffer layer composed of a polymer doped with an electron acceptor [tris(4-bromophenyl)aminium hexachloroantimonate] was found to improve the surface roughness of the anode, particularly when the layer was sufficiently baked at a high temperature to transform it into the glass phase. The phase transition of the layer into the glass phase also affected its electric properties. Despite that the baking temperature was higher than the decomposition temperature of the electron acceptor, the resistivity of the layer with a smooth surface was one order of magnitude lower than that of the undoped layer.