The VUV double photoionizations of small molecules （NO, CO, CO2, CS2, OSC and NH3） were investigated with photoionization mass spectroscopy using synchrotron radiation. The double ionization energies of molecules were determined with photoionization efficiency spectroscopy. The total energies of these molecules and their parent dications （NO^2＋,CO^2＋,CO2^2＋, CS2^2＋, OSC^2＋and NH^2＋） were calculated using the Gaussian O3 program and Gaussian 2 （NO^2＋, CO^2＋, CO2^2＋,CS2^2＋,OSC^2＋ and NH3^2＋） were calculated using the Gaussian 03 program and Gaussian 2 calculations. Then, the adiabatic double ionization energies of the molecules were predicated by using high accuracy energy mode. The experimental double ionization energies of these small molecules were all in reasonable agreement with their respective calculated adiabatic double ionization energies. The mechanisms of double photoionization of these molecules were discussed based on a comparison of our experimental results with those predicted theoretically. The equilibrium geometries and harmonic vibrational frequencies of molecules and their parent dications were calculated by using the MP2 （full） method. The differences in configurations between these molecules and their parent dications were also discussed on the basis of theoretical calculations.
