Two zero-dimensional inorganic-organic hybrids, namely, [C4mim][Cd(TCDPPA)3] (1) and [C4mpy][Cd(TCDPPA)3] (2), where (TCDPPA)- = 2,2,2-trichloro-N-(di(pyrrolidin-1-yl)phosphoryl)acetamide, (C4mim)+ = 1-butyl-3-methylimidazolium, and (C4mpy)+ = 1-butyl-4-methylpyridinium, have been synthesized via metathesis reactions and characterized systematically. These ionic cadmium-containing inorganic-organic hybrid compounds are assembled from a bulky organic cation and a complex anion constructed from the chelation of three TCDPPA ligands to one cadmium ion. These compounds possess wide band gaps and emit in the deep-blue region intensely with a quantum yield as high as 34.04%. The success of this work provides a new method for the design and fabrication of high-efficiency blue-emitting materials.