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Two new sporopollenin-immobilized Schiff bases, S-[N-(2-aminoetil) salicylaldiimino] and S-[N-(2-aminoetil) benzaldiimino], and their cobalt (Ⅲ) and nickel (Ⅱ) complexes, S-[N-(2-aminoetil) benzaldiimino] aquatriacetato cobalt (Ⅲ), S-[N-(2-aminoetil) salicylaldiimino] aquadiacetato cobalt (Ⅲ), S-[N-(2-aminoetil) benzaldiimino] diacetato nickel (Ⅱ), and S-[N-(2-aminoetil) salicylaldiimino] diacetato nickel (Ⅱ), were synthesized onto a chemically modified sporopollenin with ethylenediamine. The immobilized ligands and their metal complexes were characterized by thermal analysis and spectroscopic techniques such as infrared, ultraviolet-visible, and atomic absorption spectrometry. Immobilized Schiff base metal complexes, S-[N-(2-aminoetil) benzaldiimino] aquatriacetato cobalt (Ⅲ) and S-[N-(2-aminoetil) salicylaldiimino] aquadiacetato cobalt (Ⅲ), were used as ligand exchanger media to investigate ligand adsorption behavior of methylene blue (MB) with column technique. The result shows that the chelation of methylene blue with S-[N-(2-aminoetil) salicylaldiimino] aquadiacetato cobalt (Ⅲ) complex increases ligand adsorption capacity.