Time-resolved spectroscopy in the vacuum/extreme ultraviolet (VUV/XUV) spectral range promises to disclose ultrafast dynamics in all states of matter. Completing a measurement within a single shot eliminates the influence of experimental parameter fluctuations and enhances its statistical significance. We demonstrate a single-shot temporal metrology scheme operating in the vacuum/extreme-ultraviolet spectral range, combining few-femtosecond resolution in a wide temporal window with high detection efficiency. An anticollinear geometry encodes temporal delay information on the beam propagation coordinate. The spatial distribution of ions created in the common focus is captured with a mass/charge-state-selective ion imaging spectrometer, resulting in a single-shot pump–probe measurement. We demonstrate a proof-of-principle single-shot VUV-pump/VUV-probe experiment by investigating ultrafast dissociation dynamics of O2 excited at 162 nm. The experimental determination of the finite instrument response in the same apparatus enables robust deconvolution of the investigated dynamics well beyond the instrument’s intrinsic temporal resolution.