The compositions of trioctahedral micas from 51 samples of granitoids with different geochemical affiliations and grades of differentiation from the Bohemian Massif, Central Europe, were analysed using electron microprobe (major elements) and laser ablation inductively coupled plasma mass spectrometry (Li, Sc, Ga, Ge, Nb, In, Sn, Cs, Ta, W, Tl). The micas form a continuous evolutionary series from phlogopite to zinnwaldite. The phlogopites and biotites from the I-type rocks are characterized by 5.5–5.7 Si, 2.4–2.6 Al, <0.1 Li atoms per formula unit [apfu] and Mg/(Mg + Fe) = 0.4–0.8. The biotites from the S-type granites usually contain 5.3–5.7 Si, 3.2–3.6 Al, 0.1–0.3 Li apfu and Mg/(Mg + Fe) = 0.15–0.4. The annites and zinnwaldites from the rare-metal granites contain 5.7–6.8 Si, 3.2–3.8 Al, 0.6–2.6 Li apfu and Mg/(Mg + Fe) < 0.1. The concentrations of F, Rb, Cs and Tl increase from the phlogopites and biotites to zinnwaldites: F 0.1 → 8 wt.%, Rb2O 0.05 → 1.7 wt.%, Tl 2 → 50 ppm and Cs 40 → 2000 ppm. The concentrations of Sn, Nb, Ta and W in phlogopites and biotites from the I- and S-type granitoids generally correlate with those of the parent rocks and reach values of (in ppm) 20–100 Sn, 20–250 Nb, 1–20 Ta and <5 W. The highest concentrations were found in the Li-annites in the relatively early facies of rare-metal granites (in ppm): 250–600 Sn, 400–600 Nb, 60–120 Ta and 50–120 W. The zinnwaldites in the late rare-metal granites facies are impoverished in these elements, which is explained by contemporaneous crystallization of cassiterite and columbite. Lithium enters the crystal lattice of trioctahedral micas via the exchange vector Li3□Si3Fe−6Al−1 up to concentrations of ∼2.5 wt.% Li2O (1.5 apfu Li). At higher Li concentrations, Li is incorporated through the exchange vector Li3Si1□–1Fe–2Al–1.