A novel thermally stable tetranuclear cadmium carbonyl complex [Cd(CO)(3)(C6H3Cl)](4)center dot 2H(2)O has been synthesized for the first time through a green path with an overall yield of 35%. The synthetic route features a new pathway, creating the two ortho-positions with respect to the chlorine atom in the aryl rings for bridging two cadmium metal centers. The title complex has been characterized by microanalytical, infrared spectroscopic, and thermal methods while its structure has been established by single-crystal X-ray diffraction supported by H-1, C-13, and Cd-113 NMR data.