The phonon component of thermal diffusivity (D) was measured up to temperatures (T) of ~1000–1500 K from laser-flash analysis from four chemically distinct, gem quality single crystals and six cleavage flakes or mats of orthopyroxenes, plus synthetic protoenstatite. From electron microprobe analysis, Mg/(Mg + Fe) varies from 0.65 to 1.0 and Al, Mn, Cr, Ti, and Na occur as minor impurities. From visible spectroscopy, Fe3+ content is small to negligible. From near-IR spectroscopy, hydroxyl contents range from ~ 0 to 600 ppm. Heating large crystals redistributes H+ among various sites: thus, thermal history influences speciation. For Mg/(Mg + Fe) ~ 0.9, at 298 K, D is 1.8, 1.9, and 3.2 mm2s−1 along , , and . For all samples, D decreases with increasing T. Roughly, anisotropy is independent of T, and unaffected by transition to the protoenstatite structure, which causes D to drop by ~10 %. Low-order polynomials describe D−1(T) for orthopyroxenes. A second-order polynomial describes the dependence of D298 on Mg content. Only 300 ppm OH suffices to lowers D by ~10 % whereas Fe3+ makes D decrease more rapidly with T but coupled Al substitution has the opposite effect. Available heat capacity and volumetric data were used to calculate orthopyroxene and protoenstatite thermal conductivity.