The polycrystalline sample of complex tungsten-bronze compound Li2Pb2Sm2W2Ti4Ta4O30 was prepared by a high-temperature solid-state reaction technique. Room temperature X-ray diffraction (XRD) study suggests the formation of a single-phase compound. Microstructure of the pellet sample was studied by scanning electron microscope. The temperature variation of dielectric constant shows dielectric anomaly in the sample. Study of electrical properties (impedance, conductivity, etc.,) of the material exhibits a strong correlation between its micro-structure (i.e., bulk, grain boundary, etc) and electrical parameters. A typical Arrhenius behavior was observed in the temperature dependence of dc conductivity.