The current study describes results of the application of radial basis function-partial least squares (RBF-PLS), partial robustM-regression (PRM), singular value decomposition (SVD), evolving factor analysis (EFA), multivariate curve resolution with alternating least squares (MCR-ALS) and rank annihilation factor analysis (RAFA) methods for the purposes of simultaneous determination of trace amounts calcium (Ca2+) and magnesium (Mg2+) and exploratory analysis based on their colored complexes formation with 1-(1-hydroxy-4-methyl-2-phenylazo)- 2-naphthol-4-sulfonic acid (calmagite) as chromomeric reagent. The complex formation Ca2+ and Mg2+ with calmagite was investigated under pH 10.20. The performance of RBF-PLS model in detection of minerals was compared with PRM as a linear model. The pure concentration and spectral profiles were obtained using MCRALS. EFA and SVD were used to distinguish the number species. The stability constants of the complexeswere derived using RAFA. Finally, RBF-PLSwas utilized for simultaneous determination of minerals in pharmaceutical formulation and various vegetable samples.