This Letter reports on the observation of optoelectronic switching in addressable molecular crossbar junctions fabricated using stamp-printing method. The active medium is a self-assembled monolayer softly sandwiched between gold electrodes. The junctions are investigated through current-voltage measurements at varied temperature, which show reversible optoelectronic switching with on/off ratio of three orders of magnitude at 95 K. The switching is independent of both optical wavelength and molecular structure, while it strongly depends on the temperature. It is shown that the distinct binding nature of the molecule/electrode interfaces play a dominant role in the switching performance. (C) 2009 Elsevier B.V. All rights reserved.