A self-assembled monolayer (SAM) of a single molecule magnet (SMM) bearing a tetrairon(III) core and sulfur-containing terminal groups was exposed to aqueous solution. The effect of the chemical environment on the monolayer was investigated using cyclic voltammetry, X-ray photoelectron spectroscopy, and atomic force microscopy. The physisorbed SMM molecules desorbed and the sulfur atoms in the remaining SMM were oxidized during immersion in H2O, while the Fe(III) ions remained intact. We found that the SMM molecules concomitantly formed aggregates on the surface. These transformations caused significant changes to the redox properties of the SMM. The present research highlights the fragile nature of the SMM SAM against particular chemical environments and provides important insights into the exploitation of surface-tethered SMMs for a variety of applications. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.010210jes] All rights reserved.