Tm3+ doped Na5Lu9F32 single crystal with high optical quality was grown by an improved Bridgman method. The Judd-Ofelt intensity parameters Ωt (t=2, 4, 6) were calculated according to the measured absorption spectra and physical-chemical properties of the obtained Na5Lu9F32 single crystal. The stimulated emission cross-section of the 3F4→3H6 transition (~1.8 μm) is 0.35×10-20 cm2 for Tm3+ doped Na5Lu9F32 single crystal. The emission spectra under the excitation of 790 nm laser diode (LD) and fluorescence lifetime at 1.8 μm were measured to reveal the fluorescence properties of Tm3+ doped Na5Lu9F32 single crystal. The research results show that the Tm3+ doped Na5Lu9F32 single crystal has larger stimulated emission cross-section compared with other crystals. All these spectral properties suggest that this kind of Tm3+doped Na5Lu9F32 crystal with high physical-chemical stability and high-efficiency emission at 1.8 μm may be used as potential laser materials for optical devices.