The anodization of pure aluminum (Al) thin films of 0.5 μm thick on Titanium nitride/Silicon (TiN/Si) substrate in the lithium-based electrolytes at 2.5 V was performed to form porous and mesh morphologies of alumina–lithium composites. The electrochemical analysis through the anodization process and the morphology using a scanning electron microscope of the obtained porous alumina–lithium composites were discussed. The anodization of Al/TiN/Si films in lithium-based elec trolytes resulted in the synthesis of ultra-thin walls porous anodic alumina (PAA) with incorporated lithium ions confirmed by Raman spectroscopy. The impedance spectroscopy was performed to study the influence of incorporated lithium ions into the PAA matrix on its electronic properties. The impedance spectroscopy analysis revealed an improvement in the electri cal impedance of the formed PAA compared to the insulated alumina. In addition, its impedance data show a capacitance behavior with a low series resistance value which can be exploited for high-performance battery applications.