We report our investigations into the fabrication of nanostructures of poly(p-phenylene vinylene) via direct scanning near-field lithography of its soluble precursor. Our technique is based on the spatially selective inhibition of the precursor solubility by exposure to the ultraviolet optical field present at the apex of commercially available, Au-coated near-field probes with aperture diameters between 40 and 80 nm (+/-5 nm). After development in methanol and thermal conversion under vacuum we obtain features with a minimum dimension of 160 nm. We analyse our results via tapping-mode atomic force microscopy, and find a clear phase contrast between the core and the centre of the lithographed features, corroborating the hypothesis that hard, fully insolubilised regions are surrounded by a gel-like phase, which we estimate of the order of 110-130 nm for the smallest features, by comparing our experiments with simulations carried out using a Bethe-Bouwkamp model. Use of such model also allows us to discuss the influence of probe size, tip-sample distance, and film thickness on the resolution of the lithographic process. We demonstrate the use of the technique for the direct writing of two-dimensional periodic structures with intentional defects and a periodicity relevant to applications in the visible range.