This paper reports an unprecedented trifunctionalization of tertiary enaminones for the synthesis phosphoryl nitriles by the reactions of enaminones with diarylphosphine oxides and trimethylsilyl cyanide (TMSCN) without the use of any metal reagent. Employing tetrabutyl ammonium hydroxide (TBAH) as the catalyst (0.2 equiv) enables discrete cyanophosphonation. On the other hand, selective proximal cyanophosphonation has been realized in the presence of acetic acid only (AcOH).