In order to improve adsorbing performance and stability of chitosan in acid simultaneously, cross-linking was employed after the protection of amino groups for improving its stability, then the protection of amino groups was removed and protonated to obtain high adsorption performance. With formaldehyde as amino-group protective agent and glutaraldehyde as cross-linking reagent, cross-linked chitosan(CCTS) was prepared by reversed phase suspension method in this paper, then it was protonated to make protonation modified chitosan adsorbent(P-CCTS). The adsorption performance of sulfate ion onto P-CCTS was firstly studied and investigated by static adsorption test. Elemental analysis by energy dispersive spectrometer of X-rays (EDS) and identifying of functional groups by Fourier transform infrared spectroscopy (FTIR) were used to analyze the preparation and adsorption of the adsorbent, and the reaction mechanism of cross-linking and adsorption was investigated. The results show that the adsorption performance of P-CCTS towards sulfate ion is 10 times higher than that of unmodified chitosan, and formaldehyde and glutaraldehyde mainly react with amino (—NH2) and part of hydroxy (C6—OH) of chitosn. A salt of chitosan protonated amino chlorine was formed through the process of the protonation of amino, the adsorption of sulfate ion mainly occurs on the protonated amino on which ion exchange happened between chlorine ion and sulfate ion.