A novel red-emitting phosphor Ca5Ga6O14:Eu3+ has been synthesized using solid-state method. The excitation and emission spectra show that the phosphor can emit the red light with the main peak at 611nm under excitation of the 280 and 393nm UV chip and the optimal Eu3+ concentration is determined to be x=0.07. Analysis of emission spectrum shows that Eu3+ occupy the center of noninversion symmetry. With the increase of Eu3+ doping concentration, the decay time is prolonged due to deeper energy trap arising from nonequivalent substitution. Additionally, the measured thermal stability with 0.539eV activation energy and calculated 90.5% color purity of optimal phosphor indicate that the phosphor has an enormous application potential in w-LEDs industry.