Nanocrystalline antimony chalcogenides belong to a class of materials that offer significant potential for photovoltaics, display and lighting applications. However, a lack of synthetic methodologies that allow facile solution-based access to these nanomaterials currently restricts their practical use. Herein, a new synthetic route for the controlled preparation of antimony selenide nanostructures through colloidal chemistry is reported. A collection of nanostructures ranging from nanorods and nanocrystals to hollow spheres was successfully synthesized through the reported methodology, for which the morphological control during the particle formation was accomplished through both modulation of ligand chemistry for passivating the nanocrystal surface and accurate adjustment of the precursor ratio.