One of the priorities in the field of hydrogen energy is the development of intermediate-temperature (IT-SOFCs) and low-temperature solid oxide fuel cells (LT-SOFCs), which are capable of highly efficient operation in the range of 500–800 °C. The currently applied 8-YSZ electrolytes are expected to be replaced by one based on tetragonal zirconia (3Y-TZP), which is characterized not only by high ionic conductivity below 700 °C, but also significantly higher mechanical strength. One of the candidates is alumina-toughened zirconia (ATZ) with extraordinary mechanical properties (flexural strength of up to 1 GPa and outstanding fracture toughness (KIc) in excess of 10 MPa m0.5). A series of composites with a nanometric alumina content of 2.3, 10, and 20 vol% were obtained and investigated to evaluate the effects of aluminum addition on the electrical properties of the materials in relation to their microstructure, chemical and phase composition. Measurements performed by means of electrochemical impedance spectroscopy over the range of 300–650 °C showed that the total electrical conductivity of the obtained ATZ samples decreased slightly with increasing content of alumina inclusions and it was around one-third of an order of magnitude lower than that of the reference 3Y-TZP sinter prepared from the commercially available oxide powder containing 3 mol% of yttrium oxide (TOSOH). This is a consequence of the fact that ATZ sinters exhibited a lower specific conductivity of grain boundaries than 3Y-TZP whilst having comparable electrical conductivity of grain interiors. The total electrical conductivity values determined for the ATZ sinters at 700 and 800 °C are approximately the same as the electrical conductivity of 3Y-TZP, and they can therefore be considered a viable alternative to 8-YSZ electrolytes in applications such as IT-SOFCs or LT-SOFCs.