A large number of one-dimensional bundles of ZnSe nanowires with diameters ranging from 15–20 nm and lengths of up to tens of micrometers have been prepared via the thermal treatment of a ribbon-like precursor (ZnSe·3ethylenediamine), which has been synthesized by a mixed solvothermal route, in an argon atmosphere. The as-obtained precursor has been characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), IR spectroscopy, thermogravimetric analysis, and elemental analysis. XRD and high-resolution TEM characterization reveal that the as-synthesized ZnSe nanowires have the single-crystal hexagonal wurtzite structure with the  growth direction. The surface chemical composition of ZnSe nanowires has been studied by X-ray photoelectron spectroscopy. The cooperative action of the mixed solvents may be responsible for the formation of the morphology of the resulting products. Room-temperature photoluminescence measurements indicate the as-grown ZnSe nanostructures have a strong emission peak centered at 587 nm and two weak emission peaks centered at 435 and 462 nm. The strong emission from the ZnSe nanostructures reveals their potential as building blocks for optoelectronic devices.