ZnO nanoarrays were grown via a low-temperature hydrothermal method. Solutions, each with different additive combinations, were prepared and evaluated. The effects of the additives involved in the growth procedure, i.e., ammonium hydroxide and sodium citrate, were studied in terms of the morphological, optical and scintillation properties of the ZnO nanostructures. Measurement of the nanorod (NR) length, corresponding photoluminescence (PL) and scintillation spectra and their dependence on the additives present in the solution are discussed. ZnO NRs grown on a silica substrate, whose UV transmission was found to be better than glass, showed high-quality structural and optical properties. It was found that the addition of sodium citrate significantly reduced defects and correspondingly increased the intrinsic near-band-edge (NBE) UV emission intensity at ~380 nm. To obtain high-quality nanostructures, samples were annealed in a 10% H2 + 90% N2 atmosphere. The anneal in the forming gas atmosphere enhanced the emission of the UV peak by reducing defects in the nanostructure. NRs are highly tapered towards the end of the structure. The tapering process was monitored using time growth studies, and its effect on PL and reflectance spectra are discussed. A good alpha particle response was obtained for the grown ZnO NRs, confirming its potential to be used as an alpha particle scintillator. After optimizing the reaction parameters, it was concluded that when ammonium hydroxide and sodium citrate were used, vertically well-aligned and long ZnO nanoarrays with highly improved optical and scintillation properties were obtained.