Measurement of the photofragment velocity and angular distributions from the photodissociation of N,N-dimethylformamide at 193 nm in its nb * absorption evidences three competing dissociation channels: HCON͑CH 3 ͒ 2 →HCO(X 2 AЈ)ϩN͑CH 3 ͒ 2 (X 2 B 1); HCO(X 2 AЈ)ϩN͑CH 3 ͒ 2 (Ã 2 A 1); and HCONCH 3 ϩCH 3. ͑H atom eliminations are not probed.͒ These products are formed in a ratio of 0.15Ϯ0.04:0.49Ϯ0.09:0.36Ϯ0.07, determined by use of trimethylamine as a calibrant molecule. Nitrogen-carbonyl bond fission occurs on a rapid time scale with an angular distribution of the dissociation products given by ϭ1.2Ϯ0.2. Excited state N͑CH 3 ͒ 2 products are formed quasidiabatically from the initial planar geometry, whereas symmetry-breaking vibrations allow one-electron matrix elements to couple the initial electronic configuration to the ground state N͑CH 3 ͒ 2 ϩHCO channel. Competition of nitrogen-methyl bond fission is evidence of the strong coupling between the nb * excitation and the nitrogen-methyl reaction coordinate; ab initio calculations confirm that the electronic excitation is not localized on the N-CϭO moiety. We also include here an advance report of the excited state energy of the N͑CH 3 ͒ 2 (Ã 2 A 1) radical, which is found to be 1.59 eV.