The dehydration and decomposition of South African pyrophyllite were studied in the pressure range 2.5–5.0 GPa and in the temperature (T) range 295–1473 K using both in situ electrical conductivity measurements and X-ray diffraction studies on the recovered samples. Activation energies for conduction (Qc) vary in the range 0.02–0.07 eV for T ≤ 500 K where the dominant conduction mode is electronic, and Qc is in the range 1.10–1.28 eV for T ≥ 500 K where ionic conduction dominates. Abrupt changes in the isobaric temperature dependence of conductivity mark the onset of dehydration and subsequent decomposition into kyanite plus quartz–coesite. At 2.5 GPa, South African pyrophyllite forms the dehydroxylate phase at 760 K with a pressure dependence of ~30 K/GPa and complete decomposition follows at 1080 K with a pressure dependence of ~41 K/GPa. The resulting pressure–temperature phase diagram is in very good agreement with many previous studies at 1 atm (101.325 kPa).