Abstract A possibility of transcyclopalladation on silica gel was shown using reactions of acetato- and chloro-bridged dimeric cyclopalladated complexes derived from N,N-dimethylbenzylamine with benzyl methyl sulfide, benzyl phenyl sulfide, benzyldiphenylphosphine, 8-methylquinoline and 1,3-bis(methylthiomethyl)benzene in the presence of equimolar amount of CF3CO2H. The reaction provided the corresponding C,S-, C,N-, C,P- and S,C,S-palladacycles in 39–65% yield.