Poly(2,5-dimethoxyaniline) (PDMOA) and its copolymers with aniline (PADMOA), which exhibit remarkably improved solubility in common organic solvents, were obtained by chemical polymerization, and characterized by a host of physical techniques. The lowering of the quinoid absorption in the IR spectra and the upshifting of the N_1s envelope in the XPS spectra indicate residual doping in the XPS polymers and thermal characteristic of the polymers provide evidence for hydrogen bonding, which appear to enhance the thermal stability of the homopolymer. These polymers are highly planar and conjugated, with well-developed polaronic features, shown by the XRD, ESR and UV-spectral data. The conductivity, however, is not high and apparently may be due to localization of polaronic charges at the hydrogen-bonding sites and the increased proportion of the insulating methoxy component in the polymer matrix.