Aromatic nucleophilic substitution reaction of 1-fluoro-2,4-dinitrobenzene with para-substituted and metasubstituted anilines was kinetically investigated in the mixtures of ethyl acetate and methanol at room temperature. The correlation of second-order rate coefficients with Hammett's substituent constants yields a fairly linear straight line with negative slope in different mole fractions of ethyl acetate-methanol mixtures. The measured rate coefficients of the reaction demonstrated a dramatic variation in ethyl acetate-methanol mixtures with the increasing mole fraction of ethyl acetate. Linear free energy relationship (LFER) investigations confirm that polarity has a major effect on the reaction rate whereas the hydrogen-bonding ability of the media has a slight effect on it. Nonlinear free energy relationship based on preferential solvation hypothesis showed differences between the microsphere solvation of the solute and the bulk composition of the solvents, and non-ideal behavior is observed in the trend of the rate coefficients, which cover the LFER results. a Standard deviation. b Intercept of the single or multiparameter correlation. c e, a, and b are the coefficients of E N T , α, and β, respectively. ETHYL ACETATE-METHANOL MIXTURES