- Electron spectroscopy for chemical analysis (ESCA) is a powerful tool for the quantitative analysis of the composition and the chemical environment of molecular systems. Due to the lack of compatibility of liquids and vacuum, liquid-phase ESCA is much less well established. The chemical shift in the static ESCA approach is a particularly powerful observable quantity for probing electron orbital energies in molecules in different molecular environments. Employing high harmonics of 800 nm (40 eV), near-infrared femtosecond pulses, and liquid-water microbeams in vacuum we were able to add the dimension of time to the liquid interface ESCA technique. Tracing time-dependent chemical shifts and energies of valence electrons in liquid interfacial water in time, we have investigated the timescale and molecular signatures of laser-induced liquid-gas phase transitions on a picosecond timescale.