Several atmospheric lidar techniques rely on the exact knowledge of the spectral line shape of molecular scattered light in air, which, however, has not been accurately measured in real atmosphere up to now. In this paper we report on the investigation of spontaneous Rayleigh-Brillouin scattering within the atmosphere, utilizing horizontal lidar measurements (λ=355 nm, θ=180°) performed from the mountain observatory Schneefernerhaus (2650 m), located below Germany's highest mountain, the Zugspitze. These lidar measurements give proof of the effect of Brillouin scattering within the atmosphere for the first time to our knowledge. The measurements confirm that the Tenti S6 model can be used to adequately describe spontaneous Rayleigh-Brillouin spectra of light scattered in air under real atmospheric conditions. The presented results are of relevance for spectrally resolving lidars like those deployed on the Atmospheric Dynamics Mission Aeolus (ADM-Aeolus) andthe Earth Clouds, Aerosols, and Radiation Explorer Mission (EarthCARE).