Extraction equilibria of the systems (water + pyruvic acid + alcohol/Alamine 336) have been investigated at T = 293.2 K. The solvent mixture of 1-dodecanol/alamine yields the largest separation factors for the extraction of pyruvic acid. An analytical structure for optimum extraction has been developed as the locus of the proposed separation factors. The properties of extraction systems have been correlated by a solvation relation (SERLAS) with 5 and 10 parameters. The tie-lines of the present systems have been predicted by the universal functional activity coefficient (UNIFAC) original model. The reliability analysis of both models has been made statistically against the experimental extraction factors.