The ground state equilibrium structure and electric properties of two structural isomers of donor-acceptor substituted sesquifulvalene have been calculated at ab initio HF and MP2 levels for different conformations. The electronic properties of low lying excited singlets are calculated by using CI calculations including single excitations only. Isomer I in which the inter-ring charge transfer (CT) is reinforced in the presence of substituents shows sudden polarization in the ground and two lower lying excited states, while isomer II in which the longitudinal CT interaction is attenuated does not exhibit sudden polarization. The phenomenon of sudden polarization has been rationalized in terms of the easy polarization, smaller rotational barrier, and enhanced inter-ring CT on going from the planar to the orthogonal geometry. The appreciably large static second-order polarizability of I stems from its sudden polarized ground state. The solvent (using the conductor-like polarizable continuum model (CPCM)) plays a significant role on the modulation of ground and excited state electronic properties which, in general, predicts blue-shifts for I. However, for molecule II, the two lower energy transitions show a red-shift while the others show a weaker blue-shift at any conformation.