Perylene chromophores were adsorbed on the Ag(1 1 0) surface via surface bond formation of the -CH2-SH group that was covalently attached to the perylene moieties. The lowest excited singlet state of perylene was populated with a laser pulse of 440 nm wavelength. The decay of this donor state due to ultrafast electron transfer to the Ag electrode was probed with a second, delayed laser pulse centered at 280 nm that gave rise to a photoemission signal detected in ultra-high-vacuum by a spectrometer. The fit to the measured data revealed a time constant of 15 fs for the electron injection reaction. (c) 2007 Elsevier B.V. All rights reserved.