This article reports the synthesis and purification of nanosilica (SiO2) derived from the husk of some rice varieties; Faro-44, Faro-46, Faro-52, Nerica-I, and Nerica-II. The husks were pretreated with H2O and HCl. From the measurement results, Nerica-I rice husks produced the highest silica yield and best photophysical properties. Thus, the husks of Nerica-I rice were further pretreated with H3PO4 to additionally remove more mineral impurities and the derived nanosilica labeled nSiO2 was selected to serve as a host matrix for doping with varying concentrations of Sm3+ions. The doped nanosilica (nSiO2:xSm3+; x = 0.01, 0.05, and 0.1 molar ratios) maintained the amorphous structure of the undoped nanosilica, while the surface morphology as revealed by SEM and TEM indicates agglomerates of spherical nano-sized particles with average particle size measuring 21 nm. The Sm3+-doped nanosilica shows a large surface area measuring 198.0 m2/g. The photoluminescence excitation spectra show that near UV and blue LEDs can effectively be used as excitation sources to produce yellow and yellow-green emissions from Sm3+ ion-doped nSiO2 suitable for display applications.