The present invention relates to a polymer-supported rhodium (II) catalyst and its application, which includes addition reaction to carbon-carbon multiple bond in α-diazocarbonyl compounds, insertion reaction to C—H and X—H (X═N, O, S, Se, Si and the like) bonds, or rearrangement and additional cyclization reaction thereofA novel insoluble polymer-supported rhodium (II) complex was prepared through a ligand exchange reaction between an insoluble polymer and a rhodium (II) carboxylato complex, wherein the insoluble polymer was prepared by a copolymerization reaction of (i) a styrene derivative with substituted carboxylic acid, (ii) a stylene, and (iii) a linear alkane with both ends substituted by vinylbenzyloxy groups,Namely, a polymer-supported metal complex catalyst having the following chemical formula 1: wherein M1 and M2 are rhodium, and the like; and X is an oxygen atom, etc; and R4 is an alkyl group, and the like; and k is 1 to 15%, m is 1 to 5% relative to k+l+m, and l is the remainder; and n is 4 and others; and R1 is alkyl-2-(4′-alkyloxy phthalimido methyl), etc, R2 is phenyl, etc; R3 is 4,4′-(1,3-propyrene-1,3-dioxymethyl)phenyl, etc.