We present the first spectroscopic follow-up of bright (G<15) and distant (up to 35kpc) very and extremely metal-poor (V/EMP, [Fe/H]<-2.5) red giant branch stars from the Pristine-Gaia synthetic catalogue. Using INT/IDS observations of the calcium triplet region, we confirm that 76% of our targets have [Fe/H]<-2.5, with only 3% as outliers ([Fe/H]>-2.0), demonstrating a high success rate (77% for [Fe/H]<-2.5 and 38% for [Fe/H]<-3.0). Our chemodynamical analysis reveals that 20% of stars are confined to the disc, while 46% and 34% belong to the inner and outer halo, respectively. We associate these stars with major accretion events and identify three new bright members of the metal-poor C-19 stream, including the first found above the disc plane. Our findings refine the stream's distance (~21.5kpc) and highlight the power of chemokinematic studies of V/EMP stars. We publish a catalogue of 215 V/EMP stars with 1D spectra for future analysis.