In the present work, organic -inorganic hybrid perovskite (C₁₂H₂₅NH₃)₂PbI₄ multiple quantum well (C₁₂PbI₄ QW) embedded in porous anodic alumina (PAA) thin films on glass and aluminum substrates are investigated in detail. The porosity and the uniformly arranged structure of these films are examined using Scanning Electron Microscopy (SEM). The use of two different substrates enables the PAA templates obtained by anodization in an acid electrolyte solution to have different pore dimensions. The synthesized films are characterized morphologically using the atomic force microscopy (AFM). The crystallographic structure is examined by means of X-ray diffraction (XRD). Finally, the optical characterizations are studied using a UV-Vis-NIR spectrometer and photoluminescence (PL) measurements. The effect of the two different substrates on the impregnation of the C₁₂PbI₄ QW in the PAA is presented. Both PL and AFM studies show a better penetration of the C₁₂PbI₄ QW in the case of the Al substrate providing a wider pore diameter. It results in a better quantum confinement leading to a PL blue shift more pronounced when the C₁₂PbI₄ QW are embedded into the pores of the PAA on Al substrate.