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Alkali atoms are known to promote or poison surface catalytic chemistry. To explore alkali promotion of catalysis and to characterize discharge species in alkali-oxygen batteries, we examine coadsorption of K and O 2 on Au(111) surface at the atomic scale by scanning tunneling microscopy (STM) and density functional theory (DFT). On a clean Au(111) surface, O 2 molecules may weakly physisorb, but when Au(111) is decorated with K + ions, they chemisorb into structures that depend on the adsorbate concentrations and substrate templating. At low K coverages, an ordered quantum lattice of K 2 O 2 complexes forms through intramolecular attractive and intermolecule repulsive interactions. For higher K and O 2 coverages, the K 2 O 2 complexes condense first into triangular islands, which further coalesce into rhombohedral islands, and ultimately into incommensurate films. No structures display internal contrast possibly because of high structural mutability. DFT calculations explain the alkali-promoted coadsorption in terms of three center, cation-π interactions where pairs of K + coordinate the π-orbitals on each side of O 2 molecules, and in addition O 2 forms a covalent bond to Au(111) surface. The K promoted adsorption of O 2 is catalyzed by charge transfer from K atoms to Au(111) substrate and ultimately to O 2 molecules, forming O 2 -δ in a redox state between the peroxo and superoxo. Tunneling d I/d V spectra of K 2 O 2 complexes exhibit inordinately intense inelastic progression involving excitation of the O-O stretching vibration, but absence of a Kondo effect suggests that the magnetic moment of O 2 is quenched.