We present measurements of the Schottky barrier height on individual GaAs nanowires by means of x-ray photoelectron emission microscopy (XPEEM). Values of 0.73 and 0.51 eV, averaged over the entire wires, were measured on Cu-covered n-doped and p-doped GaAs nanowires, respectively, in agreement with results obtained on bulk material. Our measurements show that XPEEM can become a feasible and reliable investigation tool of interface formation at the nanoscale and pave the way towards the study of size-dependent effects on semiconductor-based structures.