Partially conjugated monobenzo 18-crown-6 substituted oligo (p-phenylenevinylene) (MB-OPV) was synthesized via Wittig route. Formation of the oligomer was characterized by spectral (FTIR, H-1 NMR, and C-13 NMR), elemental and gel permeation chromatography analysis. The morphology of the oligomer film of one-dimensional (1D) and three-dimensional (3D) architectures were observed using atomic force microscopy. The oligomer showed excellent photoluminescence (PL) of bluish green emission at shorter wavelength of 542 nm. Stability of the polymer and glass transition temperature was determined by TGA/DSC. The dielectric properties such as dielectric constant and loss factor for the oligomer have also been studied with respect to change of frequency (50 Hz-5 MHz) and temperature (30-90 A degrees C). The value of dielectric constant decreased with increasing frequency which indicates that the major contribution comes from orientation polarization. The value of dielectric constant increased with increasing temperature which is due to greater freedom of movement of the dipole molecular chains within the oligomer at high temperature.