Fabrication and characterization of submicron optical waveguides is one of the major challenges in modern photonics, as they find many applications from optical sensors to plasmonic devices. Here we report on a novel technique that allows for a complete and precise characterization of silica optical nanofibers. Our method relies on the Brillouin backscattering spectrum analysis that directly depends on the waveguide geometry. Our method was applied to several fiber tapers with diameter ranging from 500 nm to 3 μm. Results were compared to scanning electron microscopy (SEM) images and numerical simulations with very good agreement and similar sensitivity.