Exposure of a Au(111) surface to ethynylbenzene in solution leads to the formation of a bound monolayer. A chemisorption process occurs to give a stable layer consisting of oxygen-containing hydrocarbon species. Ethynylbenzene itself does not oxidize under the deposition conditions indicating that the gold surface facilitates the oxidation process. Calculations show that ethynylbenzene and its oxidation products phenylacetic acid and phenyloxirane have positive binding energies to the gold surface. 1,4-Diethynylbenzene also binds to Au(111) and anchors gold nanoparticles deposited from solution to form dense, semiregular arrays.