In the current study, a ternary nanocomposite (NiO–ZnO–CaO) was successfully synthesized through the co-precipitation method using Azadirachta Indica (neem) leaves extract as green approach. The characterization of prepared nanocomposite was conducted using FT-IR, XRD, SEM and EDS to determine the metal oxides absorption bands, structural properties, elemental composition, and surface morphology of the nanocomposite. FT-IR analysis revealed characteristic vibrational peaks at 621, 684, and 721 cm−1, corresponding to Ni-O, Zn-O, and Ca-O bond vibrations, respectively. XRD patterns showed distinct diffraction peaks, indicative of the hexagonal structure of ZnO and the cubic structures of NiO and CaO. EDS analysis confirmed the presence of calcium, nickel, zinc, and oxygen with weight percentages of 9.2%, 14.4%, 15.1%, and 20.9%, respectively. SEM images displayed an irregular cube like morphology with noticeable clustering within the nanocomposite. The ternary nanocomposite was employed as photocatalyst and exhibited degradation efficiency (97%) against rhodamine B dye under 180 min of irradiation time. The kinetic studies of dye on the photocatalyst surface were accurately explained by a first-order kinetics model, with all R2 > 95, signifying a strong correlation between time and dye concentration. The potocatalytic degradation mechanism of ternary nanocomposite was proposed based on band positions of of NiO, ZnO and CaO forming double type II heterojunction. Furthermore, species trapping experiments employing different scavengers were carried out, revealing the active participation of OH● and O2●─ radicals in the degradation mechanism.