The broad class of Cu(Al,Ga,In) (S,Se,Te)2 solar absorber materials when doped with Yb3+ are interesting for thin film based luminescent solar concentrator (LSC's) application. In this work the strong and broad absorption properties of co-sputtered CuGaS2 (CGS) thin films combined with the luminescent properties of Yb are reported. Energy-dispersive x-ray spectroscopy (EDS), x-ray diffraction, transmission, excitation, and temperature dependent emission as well as radiative lifetime measurements are performed on thin films with varying Cu:Ga ratios and Yb3+ concentrations. It is found that Yb3+ emission can be broadly sensitized by the host in the range of 200–600 nm. A lower Cu:Ga ratio, crystallinity and post annealing in air provides a positive impact on the sensitization of Yb3+ emission. The temperature dependent time integrated decay curves show a clear thermal energy barrier of about 0.2 eV. Because the exponential tail, with a lifetime of 110 μs, is constant with temperature, we conclude that the barrier is connected to the thermal release of electrons trapped at the Yb2+ ground state. The low energy transfer efficiency from the host to the Yb dopant is attributed to efficient non-radiative electron-hole pair recombination. The prospects and design criteria of Cu(Al,Ga,In) (S,Se,Te)2 solar absorber materials for LSC applications is the further subject of the discussion.