This work proposes the use of photo-oxidation degradation with UV radiation/H2O2 as sample treatment for the determination of Fe, Zn, Mn, Ni and Co in municipal solid waste landfill leachate by flame atomic absorption spectrometry (FAAS). Three variables (pH, irradiation time and buffer concentration) were optimized using Doehlert design and the proportions of mixture components submitted to UV radiation (leachate sample, buffer solution and H2O2 30%, v/v) were optimized using a constrained mixture design. Using the experimental conditions established, this procedure allows limits of detection of 0.075, 0.025, 0.010, 0.075 and 0.041 µg mL-1, and the precision levels expressed as relative standard (%RSD, 0.5 µg mL-1) were 3.6, 1.8, 1.3, 3.3 and 1.7%, for Fe, Mn, Zn, Ni and Co respectively. Recovery tests were carried out for evaluation of the procedure accuracy and recoveries were between 92 and 106% for the studied metals. This procedure has been applied for the analysis of the landfill leachate collected in Jequié, a city of the southwestern region of the State of Bahia, Brazil. The results were compared with those obtained by acid digestion. There was no significant difference between the results obtained by the two methods based on paired t-test at 95% confidence level.