In this work, porous anodic aluminium oxide (AAO) films were fabricated by anodization in an electrolyte mixture with various concentration ratios of malonic acid and oxalic acid at room temperature. The photoluminescence (PL) properties of the AAO films before and after annealing from 300°C to 650°C in air or vacuum conditions were investigated, showing a strong PL band in the range 300-550 nm. We observed a weak PL in the AAO film formed in the malonic acid electrolyte, whereas the films fabricated using an electrolyte mixture showed strong PL emissions, exhibiting a maximum. The broad PL band was decomposed into three Gaussian sub-bands, in which the first two sub-bands could be attributed to the luminescence centre oxygen vacancies (F+ and F defect centres), whereas the latter transformed from malonic impurities and oxalic impurities. More interestingly, the redshift of the PL bands occurred with increasing oxalic acid concentration, and the PL wavelength and intensity could be modulated by varying the concentration ratios in the malonic acid and oxalic acid electrolyte mixture.