Separation of 2,4,6-trinitrophenol (Picric acid) from aqueous solution by trioctyl amine (TOA), which is a long-chain aliphatic amine, has been studied at 298K. Diluents (alcohols) (isoamyl alcohol, octan-1-ol, decan-1-ol) have been used to dissolve TOA. Experimental results of batch extraction are calculated and reported as distribution coefficients (KD), loading factors (Z), and extraction efficiency (E). The most effective diluent has been found to be isoamyl alcohol with a distribution coefficient value of 19.333. In this article, the linear solvation energy relationship (LSER) modeling (included Hidebrand-Hansen solubility parameters) has been done on the reactive extraction of picric acid to obtain the model parameters. Modeling using an LSER model predict a close resemblance of experimental data.