In this study, the solvatochromic behavior of Methyl orange was studied visible spectrophotometrically in seven aqueous binary systems from water with methanol, ethanol, propanol, DMF, DMSO, acetone and dioxane solvents. The spectral data was interpreted in terms of solute-solvent and solvent-solvent interactions. The deviation from linearity in the plots of νmax versus x2 due to preferential solvation of the Methyl orange by one component of the mixed solvent and due to solvent microheterogeneity. The preferential solvation parameters local mole fraction X2L, solvation index δs2 and exchange constant K12 were evaluated. The preference of solute to be solvated by one of the solvating species relative to others was explained. All values of K12 were less than unity that indicates the preferential solvation of Methyl orange by water, except in case the water-propanol mixture where K12 was higher than unity. The preferential solvation index δs2 values were calculated and interpreted for each binary mixture. The magnitude of preferential solvation index was highest in water-DMSO mixtures than in the all other solvent mixtures. The energy of electronic transition in maximum absorption (ET) was calculated in each binary mixture. The extent and importance of each solute-solvent interactions to ET were analyzed by the linear solvation energy relationships using the Kamlet-Taft strategy. [ABSTRACT FROM AUTHOR]