<p>Monolayer deposition of cobalt was demonstrated on a well-ordered ring molecular array at room temperature in ultra-high vacuum by means of home-built low-temperature scanning tunneling microscopy (STM) and ultraviolet photoelectron spectroscopy (UPS) setups. Sub-monolayer cobalt (Co) was deposited on a (7×4) array of 4,4′,5,5′-tetrabromodibenzo[18] crown-6 ether (Br-CR) molecules grown on Cu(111). The adsorbed Co atoms were found to intercalate and deconstruct the well-ordered molecular structure, providing Co and Br-CR mixing clusters.</p>