This manuscript describes a facile and environmentally benign protocol for the acetylation of various alcohol and amines catalyzed by onion peel ash under a base- and solvent-free condition. Various acetates were successfully prepared from the alcohols and amines using onion peel ash as a catalyst and the end-products were obtained in good to excellent yields (76−96%). The current reported protocol complies with green chemistry principles, such as a base- and solvent-free condition, mildness of the reaction, and a recyclable catalytic system up to four times. Furthermore, the current method allows the management of the abundant onion peel bio-waste into a more useful catalyst in the field of organic synthesis. The transformations of bio-wastes into catalysts for organic reactions are of interest and highly sought after by scientists to meet the goal for a more sustainable chemistry in the near future.