Near-field scanning optical lithography (NSOL) has been used to produce arbitrary structures of the electroactive polymer polyphenylenevinylene at sizes comparable to optical wavelengths, which are of interest for integrated optical devices. The structures are characterized using AFM and SEM and exhibit interesting fine structure. The characteristic size and shape of the lithographic features and their associated fine structure have been examined in the context of the electric field distribution at the near-field scanning optical microscope tip. In particular, the Bethe–Bouwkamp model for electric field distribution at an aperture has been used in combination with a recently developed model for precursor solubility dependence on UV energy dose to predict the characteristics of lithographic features produced by NSOL. The fine structure in the lithographic features is also investigated and explained. Suggestions for the further improvement of the technique are made.