The photochemistry of three carbonyl azides was studied by ultrafast time-resolved IR spectroscopy. Benzoyl, 2-naphthoyl, and pivavoyl azides are promoted to upper excited states S-n with 270 nm excitation in chloroform. The S-n states decay in 300 fs to form both the carbonylnitrenes and the S-1 excited states. The decay of the S-1 states of the carbonyl azides correlates with the growth of isocyanates. Formation of carbonytnitrene from S-1 is at most a minor process if it happens at all. The quantum yields of azide decomposition of these azides with 270 nm light are close to unity in chloroform.