Complex impedance analysis of new tungsten bronze ferroelectric vanadates, Na2Pb2R2W2Ti4V4O30 (R = Gd, Eu), was carried out on samples prepared relatively at low temperature using a mixed-oxide technique. The formation of the materials under the reported conditions has been confirmed by an X-ray diffraction technique. A preliminary structural analysis exhibits orthorhombic crystal structure of the materials at room temperature. The electrical properties of the materials have been studied using ac impedance spectroscopy technique. Detailed studies of impedance and related parameters exhibit that the electrical properties of the materials are strongly dependent on temperature, and bear a good correlation with their microstructures. The temperature dependence of electrical relaxation phenomenon in the materials has been observed. The bulk resistance, evaluated from complex impedance spectra, is found to decrease with rise in temperature, exhibiting a typical negative temperature co-efficient of resistance (NTCR) – type behavior similar to that of semiconductors. A small contribution of grain boundary effect was also observed. The complex electric modulus analysis indicates the possibility of hopping conduction mechanism in the system with non-exponential type of conductivity relaxation. The ac conductivity spectra exhibit a typical signature of an ionic conducting system, and are found to obey Jonscher’s universal power law.