Aminophosphonium salts [Ph3PN(H)R]BPh4 (1) [R = C6H5CH2 (1a), 4‐CH3C6H4CH2 (1b), C6H5 (1c)] were obtained by allowing hydride IrHCl2(PPh3)2{P(OEt)3} to react first with triflic acid and then with the organic azide RN3. The compounds were characterized spectroscopically and by X‐ray crystal structure determination of [Ph3PN(H)CH2C6H4‐4‐CH3]BPh4 (1b). A reaction path for the formation of aminophosphonium cations is also proposed.