Ni-doped β-Ga2O3 single crystals were grown by edge-defined film-fed growth (EFG) method, and the crystal structure and quality were verified by powder X-ray diffraction (PXRD) and Laue diffraction. The effect of Ni2+ doping on optical properties of β-Ga2O3 was investigated by UV-Vis-NIR transmission spectra and infrared transmission spectra. It is found that the ultraviolet cut-off edge of (100) plane is 252.9 nm and corresponding optical bandgap is 4.74 eV. Furthermore, the broadband near-infrared luminescent property of Ni-doped β-Ga2O3 was discovered by cathodoluminescence (CL) spectroscopy in the range from 600 nm to 800 nm, which is expected to broaden the application of β-Ga2O3 crystal in broadband near-infrared.