We synthesized chalcopyrite-type (Cu1-xLix)GaS2 solid solution samples with a composition of 0.00 <= x <= 0.20 by mechanochemical process and sequential heating at 550 degrees C in 5% H2S/N-2 gas atmosphere. The X-ray powder diffraction (XRD) peaks of (Cu1-xLix)GaS2 shifted by substitution of Li atoms for Cu atoms in CuGaS2. Their crystallographic parameters were refined by Rietveld analysis using XRD data. The lattice constant a of the (Cu1-xLix)GaS2 solid solution increased with increasing Li content, x, while the lattice constant c decreased with increasing Li content, x. We determined band-gap energies of (Cu1-xLix)GaS2 solid solution by diffuse reflectance spectra. The band-gap energy of the (Cu1-xLix)GaS2 solid solution increased from 2.44 eV of CuGaS2 (x = 0.0) to 2.54 eV of (Cu0.8Li0.2)GaS2 (x = 0.2). To understand the band diagram of (Cu1-xLix)GaS2 solid solution, the energy level of the valence band maximum (VBM) was estimated from the ionization energy, which was measured by photoemission yield spectroscopy. The energy level of the conduction band minimum (CBM) was also determined by adding the band-gap energy to the VBM level. The VBM level of the (Cu1-xLix) GaS2 solid solution decreased with increasing Li content, x. On the other hand, the CBM level was approximately constant. Li-doping in CuGaS2 is effective for decreasing the VBM level without increasing the CBM level.