We report the generation of a purely vibrational Raman comb, extending from the vacuum ultraviolet (184 nm) to the visible (478 nm), in hydrogen-filled kagomé-style photonic crystal fiber pumped at 266 nm. Stimulated Raman scattering and molecular modulation processes are enhanced by higher Raman gain in the ultraviolet. Owing to the pressure-tunable normal dispersion landscape of the "fiber + gas" system in the ultraviolet, higher-order anti-Stokes bands are generated preferentially in higher-order fiber modes. The results pave the way towards tunable fiber-based sources of deep-and vacuum ultraviolet light for applications in, e.g., spectroscopy and biomedicine.Fiber delivery and frequency conversion in the ultraviolet are topics of much current interest [1,2].Step-index fibers with pure silica cores have proven unsuitable because their performance dramatically falls over time due to colorcenter-related optical damage, unless they are hydrogen loaded [3]. Recent alternatives such as fluoride fibers [4] partially resolve this problem, extending the usable wavelength range into the deep ultraviolet (DUV). Kagomé-style hollow-core photonic crystal fiber (kagomé-PCF) is excellent alternative, offering a very low light-glass overlap [5]. It has been used for stable long-term transmission of continuous-wave 280 nm DUV light [6]. Kagomé-PCFs also offer very broad spectral transmission windows, and when gas-filled provide an ideal system for nonlinear generation of light at many different wavelengths. For example, when pumped at near infrared wavelengths, broadband DUV and vacuum ultraviolet (VUV) light has been generated in gasfilled kagomé-PCF [7,8].In this Letter, we discuss the first frequency-conversion scheme involving a H2-filled kagomé-PCF pumped at 266 nm. Taking advantage of the high Raman gain of H2 in the ultraviolet (about 3 times larger than at 532 nm [9]), we generate a purely vibrational Raman comb extending from the VUV (184 nm) to the visible (478 nm) via stimulated Raman scattering (SRS) and molecular modulation [10][11][12][13]. The short-wavelength bands extend further into the VUV than in previous experiments using H2-filled kagomé-PCF with narrow-band pump lasers [14,15]. Moreover, the narrow Raman gain bandwidth, together with a narrow-band pump, results in Raman sidebands with high spectral power density-a distinct advantage over broadband sources, when it is necessary to use filters (not always available in the DUV and VUV) to select spectral bands. The system demonstrated here is very compact compared to free-space arrangements [16] and its potential tunability using different Raman-active gases makes it ideal for applications such as high-resolution spectroscopy, metrology and biology.In SRS a relatively strong pump pulse scatters off the molecules in the medium giving rise to a lower energy Stokes signal. The beat note of the pump and Stokes signals excites a Raman-active mode of the molecule (in our system, the fundamental vibrational mode of H2 with ΩR/2π ~ 125 THz). This process is acco...