Abstract Pd-catalyzed reaction of olefins is sometimes accompanied by isomerization of the Pd center along the aliphatic chain (chain walking). The chain walking reaction enables synthesis of polyolefins with regulated structure, via C-C bond formation between vinyl or vinylene groups with the carbon atom at a remote position of the olefin monomers. The chain walking reaction also allows synthesis of poly(arylene alkenylene)s by three-component polycondensation of diiodoarenes, non-conjugated dienes and nucleophiles. Polycondensation of diols, diacids, and diamines with long alkylene chain, obtained by chain-walking alkoxycarbonylation, affords long-chain polyesters and polyamides.