The rational design of multifunctional inorganic pigments relies on the manipulation of ionic valence and local surroundings of a chromophore in structurally and chemically habitable hosts. To date, the development of environmentally benign and intense violet/purple pigments is still a challenge. Here we report a family of A 3−x Mn x TeO 6 and A 3−2x Mn x Li x TeO 6 (A = Zn, Mg; x = 0.01−0.15) pigments colored by site-selective Mn 2+ O 4 yellow and Mn 3+ O 5−6 violet chromophores. Zn 2.9 Mn 0.1 TeO 6 is intense bright yellow, comparable with commercial BiVO 4 , and has better near-infrared reflectivity (∼89%) in comparison to commercial TiO 2 . The codoped Li + "activator" generates holes and chargebalanced Mn 3+ (Mn 3+ O 5−6 ), realizing a color transformation from yellow to the bright violet pigments of A 3−2x Mn x Li x TeO 6 . The most vivid Mg 2.8 Mn 0.1 Li 0.1 TeO 6 is probably the best violet pigment known to date, exhibits excellent chemical and thermodynamic stability, and demonstrates pressure-dependent stability up to 5−7 GPa, before a (reversible) phase transition to pink. Theoretical calculations revealed the correlation between site-preference occupancy and chromophore motifs and predicted a wide color gamut of pigments in Zn 3 TeO 6 -hosted 3d transition-metal ions other than manganese.