The wetting by perfluoromethylcyclohexane of a well-defined silicon grating with a channel width of 16 nm has been studied using transmission small angle x-ray scattering. Prefilling, capillary filling, and postfilling wetting regimes have been identified. A detailed comparison of the data with theory reveals the importance of long-ranged substrate-fluid and fluid-fluid interactions for determining the wetting behavior on these length scales, especially at the onset of capillary condensation and in the prefilling regime.