An electrochemical microcantilever (EMC) was used to study the intermolecular interaction of self-assembly monolayers (SAMs) with different n-alkanethiols chain lengths (n = 0, 4, 6, 8, 12, 16) on a Au-coated microcantilever surface. Comparing potential cycling and steps in NaClO(4) solution within the same potential range, the deflection rate of bare microcantilevers is much smaller for the former which revealed that potential excitation, i.e. the surface charge, played the dominant role in driving the instant and large deflection of the bare microcantilever, while the smaller deflection amplitude of the former implied that adsorption of ClO(4)( - ) had an adverse effect on the potential-induced stress. Upon adsorption of SAMs, the deflection amplitude of the microcantilever under the potential step was much smaller than that of a bare microcantilever, and linearly decreased with the chain length increasing for n ≤ 8 (the linear correlation coefficient and the slope are 0.98 and about - 10.4 nm per CH(2) unit, respectively), following a transition (8 ≤ n ≤ 12) to a stable state (n ≥ 12). The decrease of deflection amplitude and faster decay of deflection rate of the SAMs modified microcantilever under the potential step implyed increasing compactness of the SAMs with longer chains.