The solid-state method first prepared a series of Ca3TeO6:Tm3+ blue-emitting phosphors. The X-ray powder diffraction were used to analyze the phase formations and purity of Ca3TeO6:xTm3+, xNa+ (0.002 ≤ x ≤ 0.10). The detection wavelength (λem = 454 nm) and a excitation wavenlenth (λex = 359 nm) were used to study photoluminescence spectra. After the comparison of different concentration phosphors, the optimal doping one was found as 0.05. Electric multipole interaction was proposed as the mechanism for concentration quenching in Ca3TeO6 materials. Furthermore, the Ca3TeO6:0.05Tm3+ fluoresces blue with color coordinates (0.161, 0.0671). Based on these results, Ca3TeO6:Tm3+ phosphors could be promising blue-emitting materials for the white light-emitting diodes (w-LED) applications.