We present the synthesis of monodisperse cone-shaped silica colloids and their fluorescent labeling. Rod-like silica colloids prepared by ammonia-catalyzed hydrolysis and condensation of tetraethyl orthosilicate in water droplets containing polyvinylpyrrolidone cross-linked by citrate ions in pentanol were found to transform into cone-shaped particles upon mild etching by NaOH in water. The diameter and length of the resulting particles were determined by those of the initial rod-like silica colloids. The mechanism responsible for the cone-shape involves silica etching taking place with a varying rate along the length of the particle. Our experiments thus also lead to new insights into the variation of the local particle structure and composition. These are found to vary gradually along the length of the rod, as a result of the way the rod grows out of a water droplet that keeps itself attached to the flat end of the bullet-shaped particles. Subtle differences in composition and structure could also be resolved by high-resolution stimulated emission depletion confocal microscopy on fluorescently labeled particles. The incorporation of a fluorescent dye chemically attached to an amine-based silane coupling agent resulted in a distribution of fluorophores mainly on the outside of the rod-shaped particles. In contrast, incorporation of the silane coupling agent alone resulted in a homogeneous distribution. Additionally, we show that etching rods, where a silane coupling agent alone was incorporated and subsequently coupled to a fluorescent dye, resulted in fluorescent silica cones, the orientation of which can be discerned using super-resolution confocal microscopy.@en