In this contribution, a series of shape-controllable ZnO nanostructures were synthesized in ionic liquids by a simpler, only one-step, low-temperature route, and characterized by XRD, XPS, TEM, HRTEM, SAED, EDXA, SEM, FTIR, surface area measurement and photoluminescence. We mainly investigate the effect of cations of ionic liquids on the shape of ZnO nanostructures and the forming mechanism of ZnO nanostructures in ionic liquids, as well as the luminescent property and photocatalytic activity for the degradation of Rhodamine B. The results show that the longer alkyl chain at position-1 of the imidazole ring of the ionic liquid will hinder the ZnO nanostructures from growing longer, and the hydrogen bonds may play a crucial role for the directional growth of the 1 D nanocrystals. The photoluminescent study shows that the as-obtained ZnO nanostructures exhibit a unique green emission, indicating the existence of oxygen vacancies in the ZnO nanostructures. Importantly, the as-obtained ZnO nanostructures prepared in different ionic liquids show strong size/shape-depenclent photocatalysis activity for degradation of Rhodamine B, and the well-dispersed homogeneous ZnO nanoparticles and nanowires display high photocatalytic activity. The investigation of photodegradation kinetics of Rhodamine B indicates that the photodegradation process obeys the rule of a first-order kinetic equation In(C-0/C) = kt. This is the first systematic investigation on the relationship between the structure of ionic liquids. and the morphology of DO nanostructures.