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Ba 5 SmZr 3 V 7 O 30 is a new tungsten bronze structured ceramic compound prepared by substituting Zr at Ti site in Ba 5 GdTi 3 V 7 O 30 following high-temperature solid-state reaction route. The X-ray diffraction analysis of the compound confirms the formation of single-phase orthorhombic structures at room temperature. Surface morphology of the compound was studied by scanning electron microscopy. Using a Hioki LCR meter, the effects of temperature (32˚C -500˚C) and frequency (10 2 -10 6 Hz) on structural and electrical properties were studied. Detailed analysis of impedance parameters furnishes a better conception of the electrical properties and type of relaxation processes in the material. The plateau region of the Z'~ frequency plot also indicates the presence of relaxation process in the material. The bulk resistance is observed to be decreased with rise in temperature showing a typical negative temperature coefficient of resistance (NTCR) behavior.