A novel KPF-promoted green method has been developed for the synthesis of esters and amides. A wide range of carboxylic acids and alcohols or amines worked well under the developed reaction conditions, thus providing good to excellent (61-98%) yields of the corresponding esters and amides. The method worked well with bioactive substrates such as cholesterol, levulinic acid, and linoleic acid. Wide substrate scope, operational simplicity, scalability, and sustainability make this protocol a practical and economically attractive approach for the preparation of ester and amides.