Resonance enhanced multiphoton ionization (REMPI) and time of flight (TOF) mass spectrometer technique is a high-resolution and high-sensitivity spectrum-research method. In this article the vibrotation state resolution ion spectrum of the NO (X2Π,ν″,J″) from NO (A2Σ+,ν′=0,1,J′← X2Π,ν″=0,1,J″) transition γ(0,0) γ(0,1) γ(1,1) and the spin-orbit fine structure resolved ion spectrum of the atomic oxygen from the two-photo transition of O(2P3PJ″→3P3PJ′) are obtained by the laser dissociation NO2 using above method. The O(2P3PJ″=2→3P3PJ′,2P3PJ″=1→3P3PJ′,2P3PJ″=0→3P3PJ′) ion signals correspond ultravidet (UV) ionization detection laser wavelength at 225.65 nm, 226.04 nm, 226.23 nm respectively. The experimental result shows, the resolution and sensitivity of REMPI and TOF mass spectrometer technique is higher that of laser induced fluorescence method (LIF). The obtained ion spectra of NO molecule and atom oxygen are very useful experimental information for research of the NO2 photodissociation and NO molecule atom oxygen ionization dynamics.