To gain a complete understanding of the intrinsic dynamics of a molecular rotary motor requires gas-phase measurements of isolated motor molecules, free from interactions with solvent molecules. Although weakly interacting solvents are generally considered to have little influence on the shapes of molecular potential energy surfaces, differential solvation of electronic states can modify the structure and energy of conical intersections. Solvent molecules also provide an effective sink for vibrational energy relaxation, so they may modify the dynamics on the potential energy surfaces. However, there have not been any reports of gas-phase measurements of the electronic structure and dynamics of molecular rotary motors to date, most likely due to the difficulties associated with generating molecular beams of such large molecules. Electrospray ionisation has proved a very effective method for transferring large molecules into the gas-phase in deprotonated anionic or protonated cationic forms. Here, we employ electrospray-ionisation to transfer a molecular rotary motor into the gas-phase, using a carboxylic acid group attached to the stator to provide a spectator group that is easy to deprotonate. We then use anion photoelectron spectroscopy to measure the electronic structure and dynamics of the molecular rotary motor and high-level CASSCF and MS-CASPT2 (multiconfigurational second-order perturbation theory) calculations to guide the interpretation of our experimental measurements. Interestingly, we find that the initial dynamics in the gas-phase are similar to those reported in solution:22–24 they involve relaxation away from the Franck–Condon region to a rotated conformer on the excited state and internal conversion back to the ground state. Gas-phase studies such as these, alongside solution phase studies, have the potential to improve our fundamental understanding of light-activated molecular rotary motors and inform the design of photoactivated nanoscale devices.