Nanostructures decorated with perfectly ordered porous anodic aluminum oxide templates have attained recent research interest for the production of highly efficient energy storage devices. Anodic aluminum oxide porous templates were synthesized using a two-step anodization technique in this work. Pure BiFeO3 and Zr–BiFeO3 nanostructures were grown on these ordered templates by well-controlled fluoride ions assisted autoclave enclosed hydrothermal method. Crystallographic information discloses the presence of rhombohedral crystal structure with geometric space group R3c belongs to BiFeO3. The morphological analysis depicts the formation of an average pore size of approximately 75 nm in anodic aluminum oxide templates. BiFeO3 contains fibrous nanoflakes like morphology with minute content of the monoclinic zirconia phase in Zr–BiFeO3. Optical measurements demonstrate a considerable variation in absorption and bandgap of anodic aluminum oxide with the growth of nanostructures. A significant increase in dielectric permittivity from 17.17 for anodic aluminum oxide to 187.19 for Zr incorporated compositions with a relatively low tangent loss of 0.66. •Synthesis of ordered anodic aluminum oxide porous templates using two step anodization.•Autoclave enclosed hydrothermal growth of fibrous nano flakes on AAO templates.•Crystallographic and microstructural information reveals the formation of rhombohedral Al2O3.•Optical measurements demonstrate a considerable variation in absorption and band gap of AAO with growth of nanostructures.•A significant increase in dielectric permittivity was observed in Zr containing compositions.