In this paper, we present new aspects of Sm3+‐doped pure Li2CaSiO4 as a suitable candidate for white light emitting diode (WLED) applications. The samples were mainly prepared using a conventional modified solid‐state synthesis technique. The structural studies were done using X‐ray diffraction and Rietveld refinement. Instruments such as a scanning electron microscope (SEM) were used to obtain information about the morphology of the as‐prepared samples. Photoluminescence (PL) analysis of phosphor samples for variable concentrations of doping ions with variable excitations were presented. When doped with Sm3+ in host Li2CaSiO4 it emitted intense blue, green and red emissions and a more intense red emission peak (605 nm) under 408 nm excitation (near‐UV–blue). Our study shows that the as‐prepared phosphor may be useful for optical devices and mainly for WLEDs. The corresponding transitions of doping ions and concentration quenching effect were studied in detail. The 1931 Commission Internationale de l'Eclairage (x, y) chromaticity coordinates showed the distribution of spectral regions calculated from PL emission spectra and this was found (0.63, 0.36) in the red region, so the phosphor may be useful for near‐UV–blue excited WLED applications.