The hydrated electron has fundamental and practical significance in radiation and radical chemistry, catalysis and radiobiology. While its bulk properties have been extensively studied, its behavior at buried solid/liquid interfaces is still unclear due to the lack of effective tools to characterize this short-lived species in between two condensed matter layers. In this study, we develop a novel optoelectronic technique for the characterization of the birth and structural evolution of solvated electrons at the metal/liquid interface with a femtosecond time resolution. We thus recorded for the first time their transient spectra (in a photon energy range from 0.31 to 1.85 eV) in situ with a time resolution of 50 fs. The transient species show state-dependent optical transition behaviors from being isotropic in the hot state to perpendicular to the surface in the trapped and solvated states. The technique will enable a better understanding of hot electron-driven reactions at electrochemical interfaces.