A family of 1D organic/inorganic core/shell materials formed by an inner organic nanowire (ONW) conformally covered with an inorganic wide band gap semiconductor (ZnO or TiO₂) layer is presented. The developed procedure is a two‐steps vacuum methodology involving the formation of supported single crystal small‐molecule nanowires by physical vapor deposition and plasma enhance chemical vapor deposition (PECVD) of the inorganic shell. Critical characteristics of the last technique are the possibilities of low temperature and remote configuration deposition. Additionally, an initial step has to be included in order to create nucleation centers for the growth of the ONWs. The procedure and its general character in terms of the variability in organic core and inorganic shells composition and the applicability of the technique to different substrates are presented. The formation of the inorganic shell with no damage of the organic core single‐crystalline structure is demonstrated by high resolution transmission electron microscopy. The vertical alignment of the hybrid nanostructure is achieved thanks to the interaction of the 1D organic nanostructured surfaces and the glow discharge during the deposition of the inorganic shell by PECVD. The optical properties of these core/shell NWs are studied by fluorescence spectroscopy and microscopy, and their application as nanoscale waveguides in the 550–750 nm range addressed.