We studied the optical and structural properties of highly ordered arrays of surfactant-capped ZnS nanowires (NWs) and nanorods (NRs) in organic suspensions. The photoluminescence (PL) emission measured under different concentrations and postsynthesis washing cycles interestingly showed increasing emission upon decreasing nanoparticle (NP) concentration. Synchrotron small angle X-ray scattering measurements elucidated the liquid-crystal-like structure of the NPs in suspension under different concentrations and temperatures. The NWs are stacked in a simple structure with a hexagonal cross-section, whereas the structure of the NRs is more complex, resembling a smectic-c liquid crystal, and shows unusual thermal expansion versus temperature. The results point out that a certain amount of bound surfactant must be present on the NP surface to maximize the PL intensity.