The aim of this work is to understand the molecular structural properties which may justify the great observed stability of doped alkoxy polythiophenes. Infrared frequency and intensity spectroscopy and Raman spectroscopy are used as probes. Suitably synthesized oligomers with increasing chain length and preassigned chemical structure have been studied together with several model molecules. The existence of through-space and through-bond S---O interactions has been revealed. The extent of the topologically dependent perturbation induced by the charge injection by the oxygen atoms is detected and measured. The inter- and intraring delocalizations have been monitored by the observation of the softening of the strongly Raman active "amplitude mode" and by the red shift of the electronic spectra. The conformation of the side chains is trans planar in the solid state and collapses in a liquidlike premelting state before the melting of the crystal.