The surface-catalytic recombination of oxygen and nitrogen atoms to form nitric oxide was confirmed by the direct detection of product NO molecules, using single-photon laser-induced fluorescence spectroscopy. Experiments were performed from room temperature to 1200 K in a quartz diffusion-tube sidearm reactor enclosed in a high-temperature tube furnace. Atomic nitrogen was generated using a microwave discharge, and atomic oxygen was produced via the rapid gas-phase titration reaction N + NO → O + N 2 . The use of isotopically labeled titration gases 15 N 16 O and 15 N 18 O allowed for the unambiguous identification of nitric oxide produced by the O + N surface reaction. The absolute number densities of surface-produced NO were determined from separate calibration experiments using 14 N 16 O. Observed variations of the NO number density with temperature and varying O/N atomic ratios at the sidearm entrance are generally consistent with the predictions of a simple reaction-diffusion model of the sidearm reactor that includes surface-catalyzed NO production as a species boundary condition.