Li-doped Ga2O3 one-dimensional nanostructures were synthesized by thermal evaporation. The observation results of morphology show that there are plenty of one-dimensional nanostructures in the sample. Raman spectra of samples show excellent crystallinity and the Raman peaks of the Li-doped Ga2O3 have red-shifted compared to the "undoped" Ga2O3 in the low wavenumber section. Comparing the photoluminescence behavior of the two samples at room temperature, they were found to have blue light emission peaks, but the emission peak of Li-doped Ga2O3 is blue-shifted. Additionally, there is a strong red light emission peak centered at 692 nm in the spectrum of Li-doped Ga2O3.