Phenyl acetate was studied as a general reagent for highly selective N-acetylation of primary amino groups in the presence of alcohol and secondary amino groups. Two polyamines, namely 1,8-diamino-4-azaoctane (Spd) and 1,12-diamino-4,9-diazadodecane (Spm), were N,N'-diacetylated with an efficient and mild methodology.