The early stages of surface oxidation of biaxially textured Ni-W tapes were studied using thermodynamic calculations along with experimental tape oxidation at low P(O 2 ). Tape phase and chemical composition, surface morphology, and roughness were examined using x-ray diffraction (XRD), energy-dispersive x-ray analysis (EDX), secondary ion mass spectroscopy (SIMS), x-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). For a Ni 0.95 W 0.05 alloy tape, the precise position of the tape oxidation line in P(O 2 )-T coordinates was established. This line includes a break at T % 650 C that originates from the change of the W oxidation mechanism from internal oxidation to oxidation on a free surface accompanied by segregation of the alloy components in the tape near-surface region. The surface roughness of a polished tape increased drastically during internal oxidation of W; further tape oxidation did not affect the integral roughness parameters, but introduced numerous small ($100 nm) features on the tape surface comprising NiO precipitates.