Dy3+ activated Ca5Y3Na2(PO4)5(SiO4)F2 phosphor was prepared via solid state reaction and its luminescence properties were investigated. XRD patterns confirm that all samples exhibit pure apatite phase. The analysis revealed that under UV light excitation, Ca5Y3Na2(PO4)5(SiO4)F2:Dy3+ phosphor exhibit blue and yellow peaks with CIE coordinates of (0.396, 0.421) and CCT of 3916 K. The concentration quenching mechanism between Dy3+ has been investigated. Excellent thermal stability was found in this new apatite phosphor. Besides, three additional emission peaks appear under higher temperature. With increasing temperature, the emission intensity of new peaks increase, which could be contributed to 4I15/2–6Hj (j = 15/2, 13/2, 11/2) transitions of Dy3+. The abnormal thermal quenching behavior was discussed in detail.