The Buchwald-Hartwig amination of a phosphinine bearing a bromophenyl moiety was carried out using a dinuclear Ni catalyst. A variety of monoarylamines, diarylamines, and alkylamine, as well as heterocycles, were successfully converted into novel phosphinines bearing amine units. The photophysical properties of these novel phosphinines were examined, including the substituent-dependent absorption/emission features and intramolecular charge-transfer interactions.