The influence of the morphology on the electron transport properties of ZnS nanostructures has been assessed by the electrical measurements on different ZnS nanostructures. High-quality poly(vinylpyrrolidone) capped wurtzite-ZnS micro- and nanostructures have been prepared by one step hydrothermal methods at low temperatures. Detailed structural investigation based on X-ray diffraction results and morphological analyses have been carried out using field emission scanning electron microscopy, transmission electron microscopy, selected area diffraction pattern, and high-resolution transmission electron microscopy techniques. In order to examine the formation of compound ZnS, the atomic ratio of Zn to S has been found from Energy Dispersion Spectroscopy. The bandgap of the samples has been calculated from the UV-visible absorption spectra in the reflectance mode at room temperature. The dependence of size and shape on excitonic and trap-state emission features of the nanostructures has been studied from the photoluminescence (PL) studies, and the enhancement of PL intensity in 1D nanostructures has also been discussed. High yield and highly crystalline long nanorods and nanowires have been found to be best suited for advanced optoelectronic systems because they have better photoconductivity than microparticles and nanoparticles.