The crystal structure and luminescence properties of Na(Sr0.97-xCax)PO4:0.03Eu2+ (0 < x < 1.0) phosphors were studied, depending on the Ca2+ concentration. All the Na(Sr0.97-xCax)PO4:0.03Eu2+ phosphors had a hexagonal crystal structure. The excitation spectra of the prepared phosphors showed a broad band ranging from 250 to 420 nm, which arises due to the 4f-5d transitions of Eu2+ ions. Upon the excitation of 334 nm wavelength, the emission spectra showed a broad blue band ranging from 400 to 700 nm peaking at 450 nm. Among the prepared phosphors, the Na(Sr0.72Ca0.25)PO4:0.03Eu2+ showed the strongest emission intensity and could be applied as a blue emitting phosphor for UV-based w-LEDs.