Abstract Extremely metal-poor (EMP) stars are old objects that mostly formed very early after the big bang. They are rare and, to select them, we have to rely on low-resolution spectroscopic or photometric surveys; specifically the combination of narrow- and broad-band photometry provides a powerful and time efficient way to select MP stars. The Pristine photometric survey is using the Canada–France–Hawaii Telescope MegaCam wide-field imager to obtain narrow-band photometry by utilizing a filter centred at 395.2 nm on the Ca ii-H and -K lines. Gaia DR 2 is providing us the wide-band photometry as well as parallaxes. Follow-up observations of MP candidates allowed us to improve our photometric calibrations. In this paper of the series we analyse MP stars observed with FORS2 at VLT. We demonstrate the Pristine calibration adopted in this work to be able to provide metallicities accurate to ±0.3 dex for MP giant stars with good parallaxes, while it performs poorly for dwarf and turn-off stars, whatever the accuracy on the parallaxes. We find some MP and very MP stars that are not enhanced in α elements. Such stars have already been found in several other searches, and a higher resolution follow-up of our sample would be useful to put our findings on a firmer ground. This sample of stars analysed has a low fraction of carbon-enhanced MP stars, regardless of the definition adopted. This deficiency could indicate a small sensitivity of the Pristine filter to carbon abundance, issue to be addressed in the future.