Metal ions present in waste samples, industrial effluents, acid mines and other aqueous media constitute a serious challenge in different human activities. Solvent extraction a technique for preconcentration, separation and identification of trace amount of metal ions coupled with multivariate chemometric technique was used for the determination of Fe(II) and Cr(III) from solutions in the presence of bis(salicylidene)ethylenediamine (SALEN). The influence of main extraction variables affecting the extraction efficiency was simultaneously studied and regression model equations illustrating the relationship between variables predicted. The extraction parameters (time of extraction, acid concentration, ligand concentration, temperature and metal concentration) were optimized using experimental designs with the contributions of the various parameters to extraction of the metal ions bound to the complexone evaluated using SPSS19.0 software. The statistically determined simulated models for the parameters were R2 = 0.946, 0.727, 0.793, 0.53, 0.53, 1.000 and F- values of 70.400, 13. 285, 15.348, 4.646 and 2.569×105 respectively for time of extraction, acid concentration, ligand concentration, temperature and metal concentration for Cr (III). For Fe (II), R2 = 0.243, 0.371, 0.519, 0.446, 1.000 and F-values of 0.964, 2.953, 4.310, 3.216 and 2.516×105 for time of extraction, acid concentration, ligand concentration, temperature and metal concentration respectively. The level of significance of the models as predicted was both lower than 5% making it feasible, efficient, reproducible and accurate. This means that metal ions at the conditions stated could be removed from waste samples, industrial effluents, acid mines and other aqueous media with extension in industrial scale application.