Fundamentally, methanol represents one of the simplest molecules for understanding extended hydrogen-bonded networks, and from a practical perspective it constitutes a very important chemical feedstock. The interaction of methanol with transition metal surfaces is of relevance to many catalytic processes. Gold-based catalysts show high selectivity for the partial oxidation of several species including, most recently, methanol. However, due to its weak interaction, it has not yet been possible to study intact methanol adsorption and ordering on any metal surface with molecular resolution. Using careful annealing treatments and low tunneling current, variable-temperature scanning tunneling microscopy, we show the basic bonding geometries of a range of hydrogen-bonded methanol structures as a function of surface coverage and temperature on Au(111). Like ice, methanol forms hexamer units; however, at all but very low coverages, chain structures dominate. Unlike the 2D honeycomb structure of ice, which is inte...