The chemical composition of unaltered biotites extracted from 18 Lower Palaeozoic metabentonites from Sweden, Norway and Scotland was determined. Discrimination based on FeO, MgO and TiO2 proved able to separate the metabentonites on the basis of their stratigraphical age. A triangular discrimination diagram using MgO, FeO and Al2O3 classified the biotites as calc-alkaline. Independent support for the discriminant power of FeO, MgO and TiO2 in biotite comes from Sr isotope ratios and Sr concentration data from cognate apatite crystals. Within this dataset Caradocian and Llandoverian metabentonites have unique biotite compositions, while Wenlockian samples can be characterized to a lesser degree. Biotite composition also supported the correlation of a pair of metabentonites from Norway known to form part of the same horizon. Biotite in metabentonites preserves the chemical signature of the host magmas in which it crystallized and can be used to discriminate between metabentonites of different ages and provenance.