A series of Eu³⁺ doped CaSiO₃/SiO₂ nano-phosphor powder of controlled grain size, crystalline structure, and chemical composition were synthesized using the microemulsion technique. XRD profiles of samples sintered over 600 of suggested phase shift from amorphous powder grain to more ordered polycrystalline powder of triclinic type wollastonite, CaSiO₃, with preferred crystal phase orientation of (112) and tetragonal type cristobalites of SiO₂. The grain size, crystallinity, and chemical composition of the host matrix, activator and sensitizer strongly affected both the absorption and emission bands of these samples. The amplitude of both the orange and red emission bands significantly increased with sintering temperature. The emission band is red-shifted with decreasing grain sizes. These bands displayed good sensitivity to ionic concentration of the Si⁴⁺, Ca²⁺, and Eu³⁺. With increasing Ca²⁺ ion concentration both the intensity of the red photoluminescence (PL) band increased and a concentration quenching observed. Increase in Si⁴⁺ ion concentration led to quenching in PL intensity of both the orange and red bands whereas the amplitude of the blue-band slightly increased. With increasing Eu³⁺ ion concentration the red-band initially increased whereas it started decreasing at higher sample concentration. In the presence of Ca²⁺ ion as a sensitizer, the sample showed a remarkable PL property—including—about 100% photon conversion efficiency and a two-fold increase in excitation and emission photons.