<p>Banana peel ash has attracted great interest of the academic community since this agrowaste can be either transformed into value-added products or applied as an efficient promoter in chemical reactions. In particular, the use of Water Extract of Banana peel ash (WEB) in synthetic organic chemistry has provided great advances on environmental point of view. In this study, the composition of banana peel ash has been determined using Inductively Coupled Plasma Optical Emission Spectrometry and thermogravimetric analysis. Noteworthy, the banana peel ash was converted into corresponding water agrowaste extract and successfully applied as a green reaction media for the hydrophenoxylation and hydrothiolation of acetylenedicarboxylates. In general, the desired products were achieved in reasonable yields under environmentally friendly conditions. Indeed, acetylenedicarboxylates were treated with different phenols and thiols derivatives which afforded the corresponding products in 22–87% yields. Further mechanistic studies disclosed a radical reaction pathway.</p> Graphical abstract <p></p>