High-temperature, ammonium-rich white mica has been identified for the first time in deep Paleozoic (and probably older) polymetamorphic schists from the Internal Zone of the Betic Cordillera (Spain). Ammonium-rich white mica has been characterized by optical microscopy, X-ray diffraction, infrared spectroscopy, elemental analysis, electron microprobe, and scanning and transmission electron microscopy. High-temperature, ammonium-rich white mica shows some significant chemical differences with tobelite formed in hydrothermal and low-temperature metamorphic rocks. Although the average formula, Ca0.09Na0.01K0.15(NH4)0.75(Al1.70Ti0.01Fe0.26Mg0.13)(Si2.99Al1.01)O10(OH)2, is typical of a dioctahedral mica, the chemical plots reveal a clear deviation toward the trioctahedral field. Thus, the increase in Fe + Mg contents is not accompanied by the parallel increase of Si contents, characteristic of the phengitic substitution, which is characteristic of low-pressure conditions of formation. Chemical differences are also accompanied by notable differences in the optical properties, both features suggesting that the term tobelite is not appropriate for this mica. Ammonium-rich white mica relics only persist in some graphite-rich microdomains, defining the first schistosity. Textural relations indicate that this mica formed during an older pre-Alpine metamorphic episode.