A series of new Na3CaB5O10:Eu3+ phosphor was synthesized by a solid-state reaction method, and its luminescent properties were investigated. The phase formation of phosphors was confirmed by X-ray powder diffraction (XRD). The excitation spectra exhibited that the phosphors could be effectively excited by near ultraviolet (392 nm) and blue (464 nm) light, which perfectly match the emission wavelength of near-UV light-emitting diodes (LEDs). The emission spectra showed that two characteristic red emission lines peaking at 592 and 613 nm can be obtained upon 394 and 463 excitation with the chromaticity coordinates of (0.6347, 0.3649), which are due to 5D0- 7F1 and 5D0-7F2 transitions of Eu3+ ions. The effect of Eu3+ concentration on the emission spectrum of Na3CaB5O10:Eu3+ phosphor was studied. The results showed that the emission intensity increased with increasing Eu3+ concentration, and then decreased because of concentration quenching. The obtained results indicated that this phosphor could be a promising candidate for near-UV white LEDs.