Defect influences on the photoactivity of ZnO nanoparticles prepared by a powdered coconut water (ACP) assisted synthesis have been studied. The crystalline phase and morphology of ZnO nanoparticles were effectively controlled by adjusting the calcination temperature (400-700 °C). An induced transition of hybrid Zn5(CO3)2(OH)6/ZnO nanoparticles to single-phase ZnO nanoparticles was obtained at 480 °C. The morphological analysis revealed a formation of ZnO nanoparticles with semispherical (∼6.5 nm)- and rod-like (∼96 nm) shapes when the calcination temperatures were 400 and 700 °C, respectively. Photoluminescence characterizations revealed several defects types in the samples with VZn and VO+ being in the self-assembly of semispherical- and rod-like ZnO nanoparticles. The photocatalytic activity of the ZnO nanoparticles was examined by assessing the degradation of methylene blue in an aqueous solution under low-intensity visible-light irradiation (∼3 W m-2). The results point toward the self-assembly of semispherical- and rod-like ZnO nanoparticles that had significantly better photocatalytic activity (∼31%) in comparison to that of spherical-agglomerated- or near-spherical-like species within 120 min of irradiation. The possible photocatalytic mechanism is discussed in detail, and the morphology-driven intrinsic [VZn+VO+] defects are proposed to be among the active sites of the ZnO nanoparticles enhancing the photocatalytic activity.