A dense monolayer of cobalt(II) phthalocyanine, CoPc, can be formed on a gold surface by spontaneous redox deposition followed by vacuum annealing at about 110degreesC. CsCoPc(CN)(2) or KCoPc(CN)(2) in dilute (similar to10(-6) M) ethanol solution rapidly forms a dense adlayer that, when washed with ethanol, can be imaged by scanning tunneling microscopy, STM, in air. This adlayer is converted to a monolayer of CoPc by vacuum annealing as confirmed by STM and X-ray photoelectron spectroscopy (XPS). This spontaneous surface redox adsorption process represents a novel method for depositing metallorganic complexes, which are ultimately only physisorbed on gold.