The organic/inorganic hybrid nanostructural vinylsilsesquioxanes (VSSO) were prepared from the hydrolytic condensation of vinyltrimethoxysilane (VMS). The proposed formulas of VSSO were assigned with standard spectroscopic techniques, FTIR, NMR (1H, 13C and 29Si) and MALDI-TOF MS, and a generic formula of the SSO, Tn(OH)x(OR')y (x, y = 0, 1, 2...; n =1, 2...; T = RSiO1.s-(x+y)/2n). Geometric parameters (Si-O and Si-C bond lengths, Si-O-Si and O-Si-O bond angles) and total energies of the multi-structures of VSSO were calculated by a quantum mechanical investigation and molecular symmetries. According to the results of the calculation, most molecules had stabler ladder structures than the cage isomers, therefore, the most probably reasonable and optimum structure of the VSSO system was the ladder type.