Brillouin scattering has been widely exploited for advanced photonics functionalities such as microwave photonics, signal processing, sensing, lasing, and more recently in micro- and nano-photonic waveguides. Most of the works have focused on the opto-acoustic interaction driven from the core region of micro- and nano-waveguides. Here we observe, for the first time, an efficient Brillouin scattering generated by an evanescent field nearby a single-pass sub-wavelength waveguide embedded in a pressurised gas cell, with a maximum gain coefficient of 18.90 ± 0.17 m−1W−1. This gain is 11 times larger than the highest Brillouin gain obtained in a hollow-core fibre and 79 times larger than in a standard single-mode fibre. The realisation of strong free-space Brillouin scattering from a waveguide benefits from the flexibility of confined light while providing a direct access to the opto-acoustic interaction, as required in free-space optoacoustics such as Brillouin spectroscopy and microscopy. Therefore, our work creates an important bridge between Brillouin scattering in waveguides, Brillouin spectroscopy and microscopy, and opens new avenues in light-sound interactions, optomechanics, sensing, lasing and imaging.