We experimentally demonstrate efficient coupling of atomic fluorescence to the guided mode of a subwavelength-diameter silica fiber, an optical nanofiber. We show that fluorescence of a very small number of atoms, around the nanofiber can be readily observed through a single-mode optical fiber. We also show that such a technique enables us to probe the van der Waals interaction between atoms and surface with high precision by observing the fluorescence excitation spectrum through the nanofiber.