We demonstrate, for the first time, the application of rare-gas-filled hollow-core photonic crystal fibers (HC-PCFs) as tunable ultraviolet light sources in femtosecond pump–probe spectroscopy. A critical requirement here is excellent output stability over extended periods of data acquisition, and we show this can be readily achieved. The time-resolved photoelectron imaging technique reveals nonadiabatic dynamical processes operating on three distinct time scales in the styrene molecule following excitation over the 242–258 nm region. These include ultrafast (<100 fs) internal conversion between the S2(ππ) and S1(ππ) electronic states and subsequent intramolecular vibrational energy redistribution within S1(ππ*). Compact, cost-effective, and highly efficient benchtop HC-PCF sources have huge potential to open up many exciting new avenues for ultrafast spectroscopy in the ultraviolet and vacuum ultraviolet spectral regions. We anticipate that our initial validation of this approach will generate important impetus in this area.