The crystal chemistry of Ti-rich trioctahedral micas of plutonic origin, cropping out at Black Hill (South Australia) has been investigated by combining electron microprobe analysis, single crystal X-ray diffraction, Mössbauer spectroscopy and X-ray photoelectron spectroscopy. Chemical analyses have shown the samples taken to be quite homogeneous and Ti-rich (TiO2 ≈ 7 wt.%).Mössbauer investigation yielded Fe2+/Fe3+ ≈ 30. X-ray photoelectron spectroscopy analysis seems to suggest the occurrence of three Ti species: octahedral Ti4+(60%), octahedral Ti3+(26%), and tetrahedral Ti4+(14%). The analyzed sample belongs to the 1M polytype and the relevant crystal data from structure analysis are: a = 5.347(1) Å, b = 9.261(2) Å, c = 10.195(2) Å, β = 100.29° (1). Anisotropic structure refinement was performed in space group C2/m, and converged at R = 2.62, Rw = 2.80. Structural details (the c cell parameter, the off-center shift of the M2 cation towards O4, the bond-length distortions of the cis-M2 octahedron, the interlayer sheet thickness, the projection of K–O4 distance along c*, the difference <K–O>outer−<K–O>inner) support the occurrence of the Ti-oxy substitution (VIR2+ + 2(OH)− ⇌ VITi4+ + 2O2− + H2) in the sample. Analysis of structural distortions as a function of the Ti content revealed that the positions of the oxygens O3 and O4 are displaced in opposite senses along . This produces an enlargement of the M1 site with respect to the M2 site and a shortening of the interlayer distance. This trend seems to be in common with other Ti-rich 1M micas of plutonic origin.