Reactions of H atoms with N2O have two product channels yielding NH+NO and OH+N2. Both channels were observed via NH A 3Π←X 3∑ and OH A 2∑←X 2Π laser-induced fluorescence spectra. Photoinitiated reactions with N2O–HI complexes yield a much lower [NH]/[OH] ratio than under the corresponding bulk conditions at the same photolysis wavelength. For hot D-atom reactions with N2O, this effect is somewhat more pronounced. These results can be interpreted in terms of entrance channel geometric specificity, namely, biasing hydrogen attack toward the oxygen. Another striking observation is that the OH and OD rotational level distributions (RLD) obtained under bulk conditions differ markedly from those obtained under complexed conditions, while the NH as well as the ND RLD are similar for the two environments. In addition, OH Doppler profiles change considerably in going from bulk to complexed conditions, while such an effect is not observed for NH. The changes observed with the OH RLD are most likely due to OH–halogen interactions and/or entrance channel specificity. Under bulk conditions, the Doppler shift measurements indicate a large amount of N2 internal excitation (i.e., ∼25 000 cm−1) for the OH (v=0) levels monitored. This is consistent with a reaction mechanism involving an HNNO° intermediate. The hot hydrogen atom first attaches to the terminal nitrogen of N2O and forms an excited HNNO° intermediate having a relatively elongated N–N bond compared with N2O. Then the H atom migrates from nitrogen to oxygen and exits to the N2+OH product channel, leaving N2 vibrationally excited. A simple Franck–Condon model can reconcile quantitatively the large amount of N2 vibrational excitation.