A bimetal-exchanged NaY zeolite (Cu(I)-Y(III)-Y) with a desirable adsorptive desulfurization (ADS) performance was prepared and characterized by means of X-ray diffraction, specific surface area measurements, X-ray fluorescence spectrometer, X-ray photoelectron spectroscopy, thermal gravity analysis and Fourier transform infrared spectroscopy. The effect of Y(III) ions on ADS in the presence of the xylenes was investigated. Results indicated that the ADS performance of Y(III)-Y is higher than that of most reported CeY. The Y(III)-based Cu(I)-Y(III)-Y demonstrated the higher breakthrough loading than those of reported Ce(III)/Ce(IV)-based transition metal Y zeolites, showing that Y(III) ions play a promoting role in improving the ADS selectivity. For Cu(I)-Y(III)-Y, a new strong S-M interaction (S stands for sulfur, while M stands for metal) active site was formed, which might be caused by the synergistic effect between Cu(I) and Y(III). The Cu(I)-Y(III)-Y, which combined the advantages of Cu(I)-Y and Y(III)-Y, is a kind of promising adsorbent. The breakthrough loading decreased in the order of Cu(I)-Y(III)-Y > Y(III)-Y > Cu(I)-Y, and the effect of xylene isomers on the sulfur removal was in the order of ortho-xylene > meta-xylene > para-xylene, which exhibited the same trend with the bond order of xylenes.