The novel air-stable Pd 0 complex,[Pd (pp 3 S 4)(dba)](pp 3 S 4= tris [2-(diphenylphosphino) ethyl] phosphine tetrasulfide, dba= dibenzylideneacetone) was prepared as a C–C coupling catalyst. This is regenerative from the Pd 0 complex with the partially oxidized pp 3 S 4 ligand by the chalcogen-atom substitution reaction catalyzed by Pd 0 and applicable to the recyclable Pd 0 catalytic system.