Evolutionary factor analysis (EFA) and rank annihilation factor analysis (RAFA) were applied to resolve the two-way equilibrium spectrophotometric data belonging to the complexes of Fe(III), Al(III) and V(V) with morin (3,5,7,20,40-penta hydroxy flavone) as chelating agent in triton X-100 micellar media. Then, partial least square regression combined with genetic algorithm for wavelength selection (GA-PLS) was used for simultaneous determination of the metal ions. The parameters controlling behavior of the system were investigated and optimum conditions were selected. The predictive abilities of partial least squares regression (PLS) and genetic algorithm-partial least squares regression (GA-PLS) were examined in simultaneous determination of ternary mixtures of metal ions over the concentration range of 17.0–170.0 ng ml−1, 25.0–180.0 ng ml−1 and 40.0–325.0 ng ml−1 for Fe(III), Al(III) and V(V), respectively. The relative standard errors for prediction of the ions in synthetic mixtures were lower than 5% and the mean recoveries in the tap water spiked samples were 104.2 and 101.7% for PLS and GA-PLS, respectively.