Herein, we demonstrate the first use of Nafion as heterogeneous catalyst in O-metalation of compounds containing Si-OH moiety (silanols and POSS silanols). Our methodology permits efficient and highly selective formation of Si-O-E bonds (E = Si, Ge, B) within molecules, under mild conditions with excellent yields. This approach allows syntheses of various unsymmetrical disiloxanes, germasiloxanes and borasiloxanes, as well as introduction of a wide range of functional groups into silsesquioxanes. It is worth noting that Nafion can be reused for further experiments and its catalytic activity in this process is well-maintained for more than 10 recycling steps, without a decrease in yield or selectivity. (C) 2018 Elsevier Inc. All rights reserved.