There is growing interest in using ultrafast light pulses to drive functional materials into nonequilibrium states with novel properties. The conventional wisdom is that above-gap photoexcitation behaves similarly to raising the electronic temperature and lacks the desired selectivity in the final state. Here, we report a novel nonthermal lattice instability induced by ultrafast above-gap excitation in SnSe, a representative of the IV−VI class of semiconductors that provides a rich platform for tuning material functionality with ultrafast pulses due to their multiple lattice instabilities. The new lattice instability is accompanied by a drastic softening of the lowest-frequency Ag phonon. This mode has previously been identified as the soft mode in the thermally driven phase transition to a Cmcm structure. However, by a quantitative reconstruction of the atomic displacements from time-resolved x-ray diffraction for multiple Bragg peaks and excitation densities, we show that ultrafast photoexcitation with near-infrared (1.55 eV) light induces a distortion toward a different structure with Immm symmetry. The Immm structure of SnSe is an orthorhombic distortion of the rocksalt structure and does not occur in equilibrium. Density functional theory calculations reveal that the photoinduced Immm lattice instability arises from electron excitation from the Se 4p- and Sn 5s-derived bands deep below the Fermi level that cannot be excited thermally. The results have implications for optical control of the thermoelectric, ferroelectric, and topological properties of the monochalcogenides and related materials. More generally, the results emphasize the need for ultrafast structural probes to reveal distinct atomic-scale dynamics that are otherwise too subtle or invisible in conventional spectroscopies.