Reactions of tris(trifluoromethyl)borane carbonyl, (CF3)(3)BCO, with ammonia yielded either a mixture of [NH4][(CF3)(3)BC(O)NH2], [NH4][(CF3)(3)BCN], and [NH4](2){(CF3)(3)BC(O)}(2)NH] or neat [NH4](2)[{(CF3)(3)BC(0)}(2)NH] depending on the reaction conditions, The salt K[(CF3)3BC(O)NH2] was obtained as the sole product from the reaction of NH3 with K[(CF3)(3)BC(O)F]. A simple synthesis for cyanotris(trifluoromethyl)borates, M[(CF3)(3)BCN], was developed by dehydration of M[(CF3)(3)BC(O)NH2] (M = [NH4], K) using phosgene. In addition, syntheses of the tris(trifluoromethyl)boron species [(CF3)(3)BC(O)(NHPr)-Pr-boolean AND](-), [(CF3)(3)BC(O)NMe2](-), and (CF3)(3)BC(O)NMe3, as well as of (CF3)(3)BC(O)PMe3, were performed. All species were characterized by multinuclear NMR spectroscopy. As far as neat substances resulted, IR and Raman spectra were recorded and their thermal behaviors were studied by differential scanning calorimetry. The interpretation of reaction pathways, structures, and vibrational spectra are supported by DFT calculations. The solid-state structure of K-2[{(CF3)(3)BC(O)}(2)NH]center dot 2MeCN was determined by single-crystal X-ray diffraction.