Abstract: Extremely high abundances of TiO2 (up to 12.57 wt.%) and BaO (up to 7.11 wt.%) are reported from dark reddish-brown phlogopite-biotite rims around paler phlogopite cores in a lamprophyric dyke from Ilha da Trindade, South Atlantic. Both TiO2 and BaO contents increase towards the rims of the micas and in groundmass crystals. This is accompanied by corresponding increases in FeO*, MnO and Mg number; whereas SiO2, Al2O3, Cr2O3, MgO and K2O abundances all decrease. The substitution of Ba into the biotite structure can be explained by the scheme Ba + Al = K + Si. Ti-substitution schemes however are much more complex, as no general equation can account for all the Ti incorporated into the structure and therefore several schemes are proposed.