Raman scattering enables unforeseen uses for the laser guide-star system of the Very Large Telescope. Here, we present the observation of one up-link sodium laser beam acquired with the ESPRESSO spectrograph at a resolution λ/Δλ∼140 000. In 900 s on source, we detect the pure rotational Raman lines of ^{16}O_{2}, ^{14}N_{2}, and ^{14}N^{15}N (tentatively) up to rotational quantum numbers J of 27, 24, and 9, respectively. We detect the ^{16}O_{2} fine-structure lines induced by the interaction of the electronic spin S and end-over-end rotational angular momentum N in the electronic ground state of this molecule up to N=9. The same spectrum also reveals the ν_{1←0} rotational-vibrational Q-branch for ^{16}O_{2} and ^{14}N_{2}. These observations demonstrate the potential of using laser guide-star systems as accurate calibration sources for characterizing new astronomical spectrographs.