The topic of intermolecular interactions enhancing electron tunneling between protein residues on biofilm surface has been investigated by some theoretical studies. However, few of experimental studies could confirm this viewpoint. In this work, the Mercaptopropionic acid self-assembled monolayer (MPA SAM) with terminal carboxyl groups was constructed, as a simplified model for functionalized biomimic membrane. The electron tunneling rate constant of ferrocenylmethanol redox process on SAM was obtained from experimental results of scanning electrochemical microscopy. It is found that the electron tunneling across MPA SAM is faster than that of contrastive Methyl mercaptopropionate SAM. This result is attributed to the intermolecular interactions between the redox and MPA molecules. The conditions of lower pH and weaker ion pair effect all benefit the formation of the intermolecular interactions, resulting the enhancement of electron tunneling more obvious. Based on this, this kind of intermolecular interaction is inferred to be intermolecular hydrogen bond. Our work may have contributions to exploring electron tunneling between protein residues on biofilm surface.