The dinitramide ion (N3O4-) is a relatively new simple nitrogen oxide species with previously unknown coordination chemistry. Here we report the first metal complex of N3O4-, fac-Re(bpy)(CO)(3)N3O4. As demonstrated by the infrared spectral changes upon photolysis, fac-Re(bpy)(CO)(3)N3O4 (I) is extremely photosensitive in solution and photodecomposes to fac-Re(bpy)(CO)(3)NO3 (II) and N2O (III).