The crosslinked and highly porous chitosan microspheres (EDTSC) with large pores introduced 1, 2-ethylenedisulfide moiety as a ligand were synthesized in order to apply to perfusion chromatography for recovery of precious metals. The formation of large pores in EDTSC was performed by dehydration from the oil-in-water-in-oil (O/W/O) emulsions containing chitosan in the water phase with the W/O emulsions containing sodium chloride in the aqueous phase. Both introduction of 1, 2-ethylenedisulfide moiety and crosslinking were performed at the same time by activating the high porous chitosan microspheres with 2-(chloromethyl)oxirane, followed by introducing 1, 2-ethylenedisulfide moiety with 1, 2-ethanedithiol. The microspheres possessed an average diameter of 143 µm and average pore size of 2-6 µm. The adsorption of metal ions on EDTSC was examined from hydrochloric acid by a batchwise method. EDTSC exhibited high selectivity for precious metals such as palladium (II), gold (III) and platinum (IV) over base metals in hydrochloric acid. Furthermore, the adsorption kinetics was investigated to elucidate the effect of large pores on the adsorption of palladium (II) with EDTSC. The experimental results of the adsorption kinetics indicated that the mass transfer rate in the laminar film in the aqueous phase and the chemical reaction of palladium (II) with sulfur ligand in EDTSC were the rate-determining steps at low and high concentrations of hydrochloric acid, respectively. This suggests that adsorption kinetics of palladium (II) on EDTSC is very fast, which is due to decrease in mass transfer resistance of intraparticle diffusion by effect of large pores.