Abstract: | A 2D metal–organic framework (2D‐MOF) was formed on a Cu(111) substrate using benzenehexol molecules. By means of a combination of scanning tunneling microscopy and spectroscopy, X‐ray photoelectron spectroscopy and density‐functional theory, the structure of the 2D‐MOF is determined to be Cu3(C6O6), which is stabilized by O–Cu–O bonding motifs. We find that upon adsorption on Cu(111), the 2D‐MOF features a semiconductor band structure with a direct band gap of 1.5 eV. The O–Cu–O bonds offer efficient charge delocalization, which gives rise to a highly dispersive conduction band with an effective mass of 0.45 me at the band bottom, implying a high electron mobility in this material. |