A 0.1 mol.% CoF2-doped Na5Lu9F32 single crystal with high quality in the size of ～ 10mm×100mm was grown by the Bridgman method. Three peaks located at 504, 544, and 688 nm and a broad band in the range of 1200–1600nm centered at 1472 nm were observed in the absorption spectra. The absorption peak position suggests cobalt ions in the divalent state in the grown crystal. Moreover, the cobalt ions are confirmed to locate in the distorted cubic crystal structure. Upon excitation of 500 nm light, a sharp emission peak at 747 nm ascribed to the T22(H1)→4A2(F) transition was observed for the crystal. The Co2+-doped Na5Lu9F32 crystal shows a potentially promising material for the application of a passively Q-switched laser operating in the near-infrared range.