Both ZrCl 4 and ZrOCl 2 .8H 2 O are commercially available solid chemicals. Due to their low toxicities (LD 50 [ZrCl 4 oral rate] = 1688 mg/kg), (LD 50 [ZrOCl 2 .8H 2 O oral rate] = 2950 mg/kg), low costs, ease of handling, high activity, the zirconium(IV) compounds are potential green catalysts or reagents which are of importance from different views. In this review we have paid attention to the applications of these compounds as reagents or catalysts in Friedel-Crafts reactions, Fries rearrangements, reduction and oxidation reactions, cycloaddition and hydrometalation reactions, protection and deprotection of functional groups, reactions of epoxides, iodination of alcohols, S-alkylation of thiols with alcohols, Michael addition, condensation of indoles with carbonyl compounds, Claisen ester condensation, Baylis-Hillman reaction, preparation of organozirconium compounds and some other miscellaneous reactions.