In the present paper, RbVO3 was prepared by wet chemistry synthesis from hybrid precursor. The structure of RbVO3 was characterized by X-ray diffraction (XRD) pattern and FTIR spectra. Photoluminescent (PL) properties were investigated by UV-Vis absorption spectrum and PL spectrum. In addition, the band gap of RbVO3 was calculated by using the CASTEP code with density-functional theory (DFT) method. The results indicated that RbVO3 could emit intense green-white fluorescence with peak wavelength at 525 nm and the color coordinates was (0.318 0, 0.430 9) under UV excitation at 357 nm. It was demonstrated that the theoretical result of band gap, which is 2.67 eV, agreed well with the experiment.