The novel air-stable Pd-0 complex, [Pd(PP3S4)(dba)] (PP3S4 = 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 PP3S4 ligand by the chalcogen-atom substitution reaction catalyzed by Pd-0 and applicable to the recyclable Pd-0 catalytic system.