The controllable construction and function expansion of some sophisticated aggregations represent a current hot topic in scientific research. In this paper, using a prefabricated {Co-14} cluster as a synthetic precursor, a homometallic {Co-24} and a heterometallic {Co12Cd12} giant cluster possessing similar dual [M-12] (M = Co/Cd) skeletons was prepared by reacting the precursor with excess CoCl2 and Cd(OAc)(2) salts, respectively. The detailed structural information on {Co-24} and {Co12Cd12} was characterized by single-crystal X-ray diffraction and further analyzed by X-ray photoelectron spectroscopy, inductively coupled plasma-mass spectroscopy, and scanning electron microscopy with energy dispersive X-ray (EDX) spectroscopy in the solid state. Compared to the {Co-14} precursor, magnetic difference revealed that spin-canting and magnetic ordering had been enhanced in {Co-24} and suppressed in {Co12Cd12} when dotted with diamagnetic Cd2+ ions.