A series of nanocomposites with a chemical formula of (1−x) (Al0.2La0.8TiO3) + x (BiFeO3)/ALTBF is prepared through low temperature hydrothermal method. The tetragonal phases are detected at x = 0.2 and the x = 0.4–0.8 composites show the existence of cubic phases. The transmission electron microscope pictures show the presence of well‐defined spherical particles for all composites. Furthermore, photocatalytic activity is observed for x = 0.2–0.8 composites during time intervals ranging from 0 to 240 min. The x = 0.2, 0.6, and 0.8 nanocomposites reveal the usual behavior of ac‐electrical conductivity (σac), dielectric modulus parameters (M′ and M″), and impedance parameters (Z′ and Z″). However, interestingly, x = 0.4 composite performs the negative values of electrical parameters like σac, M′, M″, and Z″. This implies that x = 0.4 composite behaves like a metamaterial possessing negative indexed electrical parameters. Therefore, x = 0.4 composite can be well suited for microwave device applications at high frequency.