Garlic peel was used as the raw material to synthesize the biosorbent for the selective recovery of precious metals from the acid chloride solution. Garlic peel is rich in carboxyl-, amino- and thiol-groups, has the potential of exhibiting high affinity to Au(III) when appropriate chemical modification process was employed. Here in the present study, the biosorbent was prepared by cross-linking garlic peel particles with concentrated sulfuric acid. Adsorption tests for mixing different metal ions such as Au(III), Fe(III), Cu(II), Ni(II) and Zn(II) from various concentrations of hydrochloric acid media indicated that Au(III) was selectively adsorbed on the cross-linked garlic peel gel over the other coexisting base metal ions investigated. The crosslinking mechanism and selective adsorption of Au(III) were also investigated briefly.