He and I and He II photoelectron spectra (UPS) of (CF3)(2)AsN3 and CF3As(N-3)(2) have been measured and assigned on the basis of HeI/HeII intensity variations, band shapes, comparison with UPS of HN3 amd (CF3)(x)AsH3-x, (x = 1, 2), and semiempirical MO calculations. The results for CF3As(N-3)(2) represent the first UPS study of a covalent diazide. They indicate that in both azides, the As 4p orbital has lost its lone pair character, being heavily mixed with the azide group orbitals.