Nanosized ZnGa2O4:Cr3+ powder is synthesized through hydrothermal method. The average particle size is 20 nm and they are spherical in shape. The excitation band from the charge transfer between Cr3+–O2− shows a blueshift behavior due to quantum confinement effect. X-ray diffraction pattern, Fourier transform-infrared spectrum, and electron paramagnetic resonance signal indicate that nanosized ZnGa2O4:Cr3+ phosphor shows many defect-related energy states and heavy lattice distortion in comparison with bulk ZnGa2O4:Cr3+ phosphor. Many defect states result in more nonradiative loss and shorter decay time.