A series of polymer-anchored Rh-Co heteronuclear carbonyl cluster catalysts was synthesized by the reaction of Co2Rh2(CO)12with various kinds of polymer supports, such as poly(2-vinylpyridine), poly(N-vinyl-2-pyrrolidone), poly(styrene-co-maleic anhydride), and aminated products of the latter. The structure of the catalysts was characterized by IR, SEM, XPS, and ICP. The influence of the support structure and crosslinking, the metal content, and the type of substrate on the catalyst's hydroformylation properties was studied. The stability of the catalysts was examined by IR. The experimental results indicate that the supported cluster catalysts possess high catalytic activity, better selectivity, good stability, and reproducibility.