The reaction of (NBu4)(2)[Pt(C=CPh)(4)] with Cd(ClO4)(2). 6H(2)O in a 1:1 molar ratio yields a white solid [PtCd(C=CPh)(4)](n) 1 (75% yield) together with yellow crystals of a very unusual decanuclear platinum-cadmium cluster [Pt4Cd6(C=CPh)(4)(mu -C=CPh)(12)(mu (3)-OH)(4)] 2 in low yield. Slow diffusion of acetonic solutions of the starting materials under aerobic conditions only produces crystals of 2 which have been shown by an X-ray analysis to be composed of a big hexanuclear cation [Cd-6(mu (3)-OH)(4)](8+) and four [Pt(C=CPh)(4)](2-) anions, held together by Pt...Cd and pi...Cd acetylide interactions, On the other hand, treatment of the insoluble product I with 1 equiv of NBu4X yields tetranuclear mixed-metal soluble complexes (NBu4)(2)[{Pt(mu -C=CPh)(4)}(2)(CdX)(2)] (X = Cl A, Br 3, CN 4), which contain two platinate. fragments connected by two CdX units through Pt...Cd and mainly Cd... C-alpha interactions. All complexes are strongly emissive in the solid state at room temperature.