Chromium-activated ZnGa2O4 nano-sized phosphor powder was prepared by the Sol-Gel technique using citric acid as chelator, and the microstructure and luminescent property were studied. The host ZnGa2O4 belongs to the spinel structure and the ZnGa2O4:Cr3+ phosphor powder exhibited bright red emission band. The excitation bands with peak of maximum height at about 250 nm, 410 nm and 560 nm were related to the charge transfer (CT) of Ga-O, 4A2-4T1 and 4A2-4T2 transitions of Cr3+, respectively. Different quenching concentrations of the CT state and intrinsic excitation were discovered originating from different energy transfer schemes. Meanwhile, with the increasing of the calcining temperature the PLE spectrum exhibited an obvious blue-shift which is attributed to the enhancement of the crystal field.