Abstract Monomeric Cu II sites supported on alumina, prepared using surface organometallic chemistry, convert CH 4 to CH 3 OH selectively. This reaction takes place by formation of CH 3 O surface species with the concomitant reduction of two monomeric Cu II sites to Cu I , according to mass balance analysis, infrared, solid‐state nuclear magnetic resonance, X‐ray absorption, and electron paramagnetic resonance spectroscopy studies. This material contains a significant fraction of Cu active sites (22 %) and displays a selectivity for CH 3 OH exceeding 83 %, based on the number of electrons involved in the transformation. These alumina‐supported Cu II sites reveal that C−H bond activation, along with the formation of CH 3 O‐ surface species, can occur on pairs of proximal monomeric Cu II sites in a short reaction time.