We have determined the valence state of Ytterbium (Yb) in a collection of meteorites covering 4–5 orders of magnitude in oxygen fugacity (fO2) by X-ray absorption near-edge structure (XANES) spectroscopy at the Yb L2 edge. In the studied meteorite minerals, Yb abundance was between 1 and 30 ppm. The data were obtained from merrillite grains (theoretical formula Ca18Na2Mg2(PO4)14) from two equilibrated ordinary chondrites (one H6 and one LL6), on oldhamite grains (theoretical formula CaS) from three EH enstatite chondrites (from EH3 to EH5) and four EL enstatite chondrites (from EL3 to EL6), on one merrilite grain and one stanfieldite grain (theoretical formula Ca4(Mg,Fe,Mn)5(PO4)6) from a pallasite, on merrillite grains from a eucrite, and in a phosphorous-bearing phase from an ungrouped primitive achondrite (NWA 11119). The obtained Yb XANES spectra were compared to those measured in terrestrial apatites (containing 17–79 ppm Yb) and in synthetic materials (metallic Yb, YbS, Yb2S3, Yb2O3). In terrestrial apatites, as well as in ordinary chondrites, in the eucrite, in the pallasite, and in the ungrouped achondrite NWA 11119, Yb is present as Yb3+ only. In enstatite chondrites, about half of the Yb in CaS is in the Yb2+ form and the fraction of Yb2+ may be slightly higher in EH compared to EL. It appears that Yb redox state can be used to build a redox scale for the most reduced objects of the Solar System as shown by this slight difference between EH and EL. However, the absence of a strong difference in Yb redox state between EH and EL chondrites suggests that the observed difference in Yb abundance anomalies in oldhamites found between EH and EL is not due to oxygen fugacity prevailing during parent-body equilibration but rather to fractionation related to volatility.