Zirconium diboride (ZrB 2 ) is an important ceramic due to its extremely high melting temperature of 3245 • C and metallic electrical conductivity, properties that make it an ideal candidate thin film electrode material for high temperature electronics. In this report, thin films of varying B:Zr ratio ranging from 3-0.67 have been grown by e-beam evaporation from elemental sources. X-ray absorption spectra at the Zr K-edge were measured before and after annealing in ultra-high vacuum for 9 hours at 1000 • C. Films with compositions near ZrB 2 stoichiometry show x-ray absorption fine structure that can be well modeled by crystalline ZrB 2 with a small portion of a coexisting tetragonal zirconia (t-ZrO 2 ) phase. Films far from stoichiometry show substantial disorder beyond the nearest-neighbor distances, and after vacuum annealing exhibit high levels of oxidation. Contributions to the x-ray absorption fine structure from a pure Zr phase are very small compared to ZrB 2 and t-ZrO 2 phases. The fact that nearly stoichiometric (3 < B : Zr < 1.6) as-deposited amorphous films form the same crystalline ZrB 2 nanostructure after annealing is particularly encouraging for high temperature thin film electronics applications, because it would allow the production of highly stable electrodes with e-beam evaporation without the need of any high temperature heating during film growth.