This study employed a wet chemistry route to synthesize submicron and luminescent CePO4:Tb3+ hollow spheres with citric acid functioning as a structure-directing agent. Citric acid amount, reaction time and temperature, and annealing temperature were found to adjust particles’ size and shape. At 20 mg of citric acid, 35 mins of reaction time at 80 oC, and 500 oC annealing temperature, the CePO4:Tb3+ particles appeared to have a well-defined hollow sphere shape and inner structure with the highest luminescent intensity. The characteristics were revealed by scanning electron microscopy images and photoluminescence spectroscopy (PL). At optimal synthesis conditions, the X-ray diffractometer recorded the crystalline phase conversion from hexagonal to monoclinic, and PL spectra revealed a green emission at 543 nm attributable to [Tb3+] 5D4 – 7F5 transition.