The absorption spectra, fluorescence spectra, and lifetimes of as-grown and annealed Cr,Yb:YAG crystal grown by Czochralski technique have been measured. The broad absorption bands in the visible region increase in intensity and shift to long wavelength after annealing, and the additional absorption around 482 nm may be possibly due to new octahedral Cr4+ center in the crystal, and the increase in the infrared (IR) region is due to the increase of Cr4+. The increase of Cr4+ also results in the groud state absorption and the concentration quenching of Yb3+ in Cr,Yb:YAG crystal after annealing, the fluorescence intensity is reduced to 75% and the emission lifetime is shortened from 1.40 to 0.44 ms.