We present the first results using a new technique that combines femtosecond pump-probe methods with energy- and angle-resolved photoelectron-photoion coincidence imaging. The dominant dissociative multiphoton ionization (DMI) pathway for NO2 at 375.3 nm is identified as three-photon excitation to a repulsive potential surface correlating to NO(C (2)Pi)+O(P-3) followed by one-photon ionization to NO+(X (1)Sigma(+)). Dissociation along this surface is followed on a femtosecond timescale.