The intermolecular hydrogen bonding between 3-mercaptopropionic acid (MPA) and ferrocenylmethanol (FcCH(2)OH) on the tip electrode was studied by scanning electrochemical microscopy (SECM). The reversible assembly and disassembly of the intermolecular hydrogen bonding were designed with the aid of the dissociation equilibrium of the terminal carboxyl groups (-COOH) of the MPA self-assembled monolayer (SAM). Based on this design, the pH-modulated assembly and disassembly of intermolecular hydrogen bonding have been implemented. The use of well-defined SAM as model membrane provides a simple yet practicable approach to explore the molecular recognition at the cell membrane surfaces. (C) 2017 The Electrochemical Society. All rights reserved.