Natural nepheline usually contains very small amounts of MgO (<0.1 wt.%), although these examples are mainly from Mg-poor alkaline igneous rocks such as nepheline syenites. However, this work shows that nepheline and kalsilite with much higher MgO concentrations can occur in the groundmass of strongly SiO2-undersaturated, feldspar-free, mafic volcanic rocks (i.e. olivine-rich foidites). Furthermore, a strong positive correlation is evident between their Mg and Fe contents. The occurrence of Mg-rich nepheline and kalsilite seems to be related to their derivation from Mg-rich magmas when compared to most of the host rocks investigated to date. Additionally, the physicochemical conditions of crystallisation seem to have an important role in the incorporation of ‘small’ divalent cations by these minerals. The prevalence of Mg-rich nepheline and kalsilite as late magmatic phases and the divergent Mg and Fe relationships for phenocrysts and ‘quenched’ groundmass crystals support this hypothesis. The positive correlation between Mg and Fe contents reflects their strong geochemical affinity and the entrance of Fe3+, Fe2+ and Mg2+ cations into the same crystallographic site of nepheline and kalsilite structures. The calculation of atomic formulae and stoichiometry parameters for nepheline-group minerals where data for the T2+ cations (e.g. Mg2+) are incorporated gives more reliable compositional parameters (see Paper 1). Calculated excess silica values (Si′) are affected significantly when the coupled substitution 2Al3+ = Mg2+ + Si4+ is considered. Thus, specific analyses of ‘small’ divalent cations are essential to obtain more realistic values of excess Si′, in particular, for nepheline and kalsilite that crystallised from Mg-rich, Si-poor, mafic–ultramafic alkaline lavas.