Ultraviolet photoemission spectroscopy (UPS) and two-photon photoemission (2PPE) spectroscopy have been employed to investigate the electronic states and the excited electron dynamics of ferrocene (Fc)terminated self-assembled monolayers (SAMs) on Au(111). For the 11-ferrocenyl-1-undecanethiol (FcC11-) SAM, an image potential state (IPS) located at E-F +3.8 eV was observed by time-resolved 2PPE. Its lifetime, 90 fs, was found to be much shorter than that of decanethiol (C10-) SAM, 11 ps. By forming the C10-SAM beforehand, the IPS lifetime for FcC11-&C10-SAM was lengthened to similar to 9 ps; this can enable improvement in molecular ordering and substantial formation of C10 domains. (C) 2013 Elsevier B. V. All rights reserved.