The Eu-doped bi-phase calcium phosphate (BCP) phosphors with (Eu + Ca)/P = 1.1, 1.3, 1.5, and 1.6 were synthesized for the first time by the precipitation method. The BCP phosphors were investigated by the X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and Photoluminescence (PL) spectra. The XRD and FTIR results indicated that BCP consisted of beta-tricalcium phosphate and hydroxyapatite phases. The PL results showed the BCP phosphors fluoresced under three visible light bands (396, 463, and 535 nm) and the strongest emission spectrum was obtained at (Eu + Ca)/P = 1.3. The PL excitated at 463 nm showed the D-5(0) -> F-7(2) transition of Eu3+ mainly generated three emission bands due to the F-7(2) energy level splitting.