The hydrated electron (e⁻(aq)) at the water/air interface has been a subject of interest due to its role in radiation chemistry and electron transfer processes. Using time-resolved electronic sum-frequency generation (SFG) spectroscopy, the study measures the electronic spectrum and dynamics of e⁻(aq) at the water/air interface following photo-oxidation of the phenoide anion. The spectral maximum agrees with that of bulk e⁻(aq), indicating that most of the orbital density resides within the aqueous phase. However, the dynamics of e⁻(aq) at the interface differ from those in bulk water, with the electron diffusing into the bulk and leaving the phenoxyl radical at the surface. The work resolves long-standing questions about the solvation of e⁻(aq) at the water/air interface and highlights its potential role in chemistry at ubiquitous aqueous interfaces. The study also discusses the implications of these findings for reactivity in microdroplets and atmospheric chemistry.The hydrated electron (e⁻(aq)) at the water/air interface has been a subject of interest due to its role in radiation chemistry and electron transfer processes. Using time-resolved electronic sum-frequency generation (SFG) spectroscopy, the study measures the electronic spectrum and dynamics of e⁻(aq) at the water/air interface following photo-oxidation of the phenoide anion. The spectral maximum agrees with that of bulk e⁻(aq), indicating that most of the orbital density resides within the aqueous phase. However, the dynamics of e⁻(aq) at the interface differ from those in bulk water, with the electron diffusing into the bulk and leaving the phenoxyl radical at the surface. The work resolves long-standing questions about the solvation of e⁻(aq) at the water/air interface and highlights its potential role in chemistry at ubiquitous aqueous interfaces. The study also discusses the implications of these findings for reactivity in microdroplets and atmospheric chemistry.