A series of new phosphors of CaAlBO4:RE3+ (RE = Ce, Tb, Eu) were synthesized by conventional solid-state reactions. The X-ray diffraction data indicate that a pure phase of CaAlBO4:RE 3+ can be successfully obtained. The photoluminescence (PL) spectra, quantum efficiency, and CIE coordinates of CaAlBO4:RE3+ were investigated. The PL and PL excitation spectra indicate that the emission wavelengths of CaAlBO4:CE3+ are 372 and 398 nm (with full width at half maximum of 33 nm) attributed to the 4f65d-4 f 7 transition of the Ce3+ activator, respectively. CaAlBO4:Tb3+ displays green emission at 483, 543, 584, and 620 nm, while CaAlBO4:Eu3+ shows a dominating emission peak at 621 nm, which is attributed to the Eu3+ 5D 0 - 7F2 transition. The quantum efficiencies of optimized CaAlBO4:Ce3+, CaAlBO4:Tb 3+, and CaAlBO4:Eu3+ were found to be 43, 21, and 19%, respectively. The phosphors may provide a new kind of luminescent material under UV excitation.