The pore height and diameter of the nanoscale structure of porous anodic alumina (PAA) film produced by the anodization technique are controllable. The structures can be applied for the fabrication of visible spectral range optical devices. In this study we characterized the luminescence properties of self-ordered PAA films evaporated onto silicon substrates. Anomalous luminescence properties produced by carrier confinement were observed in PAA films fabricated with the introduction of oxalic acid electrolytes during the anodization process. The recombination mechanisms were characterized by measuring the temperature-dependent photoluminescence (PL) spectra. The PL spectra of PAA films show an asymmetrical luminescence profile in the blue emission region. The Gaussian function divides these into two subbands. The subbands originate from two different kinds of oxygen-deficient defect centers, namely, F(+) (oxygen vacancy with only one electron) and F (oxygen vacancy with two electrons) centers. The F centers are densest at the surface but show a gradual decrease with an increase in the pore wall depth and electrolyte concentration. However, the reverse trend is observed for the F(+) centers. In strong contrast to the commonly expected trend of a uniform reduction in non-radiative recombination with decreasing lattice temperature, we observed an anomalous low-temperature PL growth and decline between the F and F(+) centers. Theoretical models corroborate the anomalous temperature behavior. All the calculations are in agreement with the experimental observations. (C) 2009 Elsevier B.V. All rights reserved.