We present new experimental calibration of V–Sc exchange between clinopyroxene, orthopyroxene, and silicate melt at physical–chemical conditions characteristic of arc magmatism. The calibration combines previously published experimental datasets with new high-pressure rapid-quench experiments conducted in a molybdenum-hafnium carbide pressure vessel assembly equipped with a custom-designed semi-permeable hydrogen membrane to control oxygen fugacity ( f O ₂ ). Experiments were performed at 200 MPa under water-saturated conditions, covering temperatures of 1030–870 °C and f O ₂ from − 1 to + 7 log units relative to fayalite-magnetite-quartz buffer (FMQ). Melt composition effects were evaluated by comparing liquid lines of descent of medium-K calc-alkaline basaltic and shoshonitic magmas. The resulting orthopyroxene-melt oxybarometer accurately reproduces f O ₂ , yielding a median absolute error of 0.36 log units over the range FMQ − 2 to + 5.5. Precise calibration of the clinopyroxene-melt oxybarometer was more challenging due to the clinopyroxene’s more complex composition and potential kinetic effects. Nevertheless, the proposed equation reproduces f O ₂ with an overall median absolute error of 1.01 log units over the calibrated range FMQ − 2.5 to + 5. Provided that the equilibrium melt composition can be constrained by the analysis of silicate melt inclusions or groundmass glass, the proposed pyroxene-melt oxybarometers can be used to track the variation of magmatic f O ₂ in diverse settings and over a broad temperature range.