Photoluminescence studies on the Ce 3+-activated borates of the type Sr 6MGa(BO 3) 6 [A = Sr; M = La, Gd, Lu; M′ = Ga; Ce 3+ at the M-site], Sr 6YAl(BO 3) 6 [A = Sr; M = Y; M′ = Al; Ce 3+ at the Y-site], LaSr 5YMg(BO 3) 6 [A = La, Sr; M = Y; M′ = Mg and Ce 3+ at the La 3+-site] have been carried out for the first time and the results are presented here. All these compounds have been synthesized by the solid state reaction under reducing atmosphere and characterized by powder XRD, TG/DT, density, particle size, SEM, FT-IR and photoluminescence techniques. The photoluminescence of Sr 6LaGa(BO 3) 6 activated with low and high Ce 3+ concentrations has been studied. The luminescence of Ce 3+ ions substituted at the larger (Gd 3+) and smaller (Lu 3+) ionic sites have been discussed. Two new compounds Sr 6CeGa(BO 3) 6 and CeSr 5YMg(BO 3) 6 have also been synthesized and studied. The photoluminescence studies show that under excitation with 254 and 355 nm, all these compounds display efficient blue emission in the region around 400–420 nm. The luminescence properties of these hexaborates under 254 nm excitation are similar to the known blue lamp phosphors Ca 5(PO 4) 3F:Sb 3+, Sr 2P 2O 7:Eu 2+, Sr 5(PO 4) 3Cl:Eu 2+ and the luminescence under 355 nm excitation are similar to the known blue TV phosphor ZnS:Ag +. Thus, the borate phosphors can be used as blue components in low pressure mercury vapor (lpmv) lamps and in television tubes.