An anhydrous orthophosphate, K3Eu5(PO4)6 (tripotassium pentaeuropium hexaphosphate), has been prepared by a high‐temperature solid‐state reaction combined with hydrothermal synthesis, and its crystal structure was determined by single‐crystal X‐ray diffraction analysis (SC‐XRD). The results show that the compound crystallizes in the monoclinic space group C2/c and the structure features a three‐dimensional framework of [Eu5(PO4)6]∞, with the tunnel filled by K+ ions. The IR spectrum, UV–Vis spectrum and luminescence properties of polycrystalline samples of K3Eu5(PO4)6, annealed at temperatures of 650, 700, 750, 800 and 850 °C, were investigated. Although with a full Eu3+ concentration (9.96 × 1021 ions cm−3), the self‐activated phosphor K3Eu5(PO4)6 shows s strong luminescence emission intensity with a quantum yield of 37%. Under near‐UV light excitation (393 nm), the series of samples shows the characteristic emissions of Eu3+ ions in the visible region from 575 to 715 nm. The sample sintered at 800 °C gives the strongest emission and its lifetime sintered at 800 °C (1.88 ms) is also the longest of all.