Two GaCl3 adducts of 4-bis(trimethylsilyl)amino-1,2,4,3,5-triazadiphosphole were formed in simple high-yielding reactions. The adducts were fully characterized (see structure of the monoadduct) and shown to be stable at ambient temperature. The structure, bonding, and NMR spectra of the triazadiphosphole adducts are discussed on the basis of MO, NBO, and DFT calculations.