Significance Laser-induced electron diffraction is a molecular-scale electron microscopy that captures clean snapshots of a molecule’s geometry with subatomic picometer and attosecond spatiotemporal resolution. We induce and unambiguously identify the stretching and bending of a linear triatomic molecule following the excitation of the molecule to an excited electronic state with a bent and stretched geometry. We show that we can directly retrieve the structure of electronically excited molecules that is otherwise possible through indirect retrieval methods such as pump–probe and rotational spectroscopy measurements.