In order to establish the electrical properties of the new solid solution Bi[Bi12-xTexO14]Mo4-xV1+xO20, impedance spectroscopy measurements have been performed. They show that the studied materials are good ionic conductors with a conductivity as high as 7.96 X 10(-3) Ohm(-1) cm(-1) at 750 degrees C for x = 1. In parallel, to check the possible phase transitions, a X-ray study between room temperature and 750 degrees C on the compositions x = 0, 1 and 2 was undertaken. Any structural changes have been observed in those oxides. The influence of the degree of substitution of Te4+ and V5+ for Bi3+ and Mo6+, respectively, has been considered.