LAUSR

V–VI antimony chalcogenide semiconductors have shown exciting potentials for thin film photovoltaic applications. However, their solar cell efficiencies are strongly hampered by anomalously large voltage loss (>0.6 V), whose origin remains controversial so far. Herein, by combining ultrafast pump–probe spectroscopy and density functional theory (DFT) calculation, the coupled electronic and structural dynamics leading to excited state self‐trapping in antimony chalcogenides with atomic level characterizations is reported. The electronic dynamics in Sb2Se3 indicates a ≈20 ps barrierless intrinsic self‐trapping, with electron localization and accompanied lattice distortion given by DFT calculations. Furthermore, impulsive vibrational coherences unveil key SbSe vibrational modes and their real‐time interplay that drive initial excited state relaxation and energy dissipation toward stabilized small polaron through electron–phonon and subsequent phonon–phonon coupling. This study's findings provide conclusive evidence of carrier self‐trapping arising from intrinsic lattice anharmonicity and polaronic effect in antimony chalcogenides and a new understanding on the coupled electronic and structural dynamics for redefining excited state properties in soft semiconductor materials.