We have shown that the combination of electrospray-ionisation, anion photoelectron spectroscopy and high-level computational chemistry calculations provides a powerful toolkit for gaining insight into the primary events that occur following photoexcitation of a unidirectional molecular motor in the gas-phase, free from solvent effects. Interestingly, the dynamics of the fluorene-based molecular motor anion that is the subject of this gas-phase study are similar to those of fluorene-based molecular motors in solution. That is, the initial dynamics are found to involve relaxation away from the Franck–Condon region to a rotated conformer on the excited state and internal conversion to a rotated conformer on the ground electronic state. It will be interesting to extend our photoelectron spectroscopy studies of rotary molecular motor anions in the gas-phase to the time-domain to measure the timescales of the dynamics and compare them with those obtained for analogous molecular rotary motors in solution. Calculations of the electronic structure and excited state dynamics of molecular rotary motors are non-trivial, so gas-phase studies provide important benchmarks for theory. Improving our fundamental understanding of photoactivated molecular rotary motors in this way is important for the future design of photoactivated nanoscale devices.