Pyruvic acid is extensively utilized in the chemical, pharmaceutical, and agrochemical industries. Novel biotechnological routes to pyruvic acid production receiving great attention and recent focus of research are toward its separation from fermentation broth or recovery from waste streams. Based on reversible complexation, extraction equilibria of the system (water + pyruvic acid + extractant/diluents) were measured at T = 308.2 K using various concentrations of pyruvic acid (0.1 kmol.m(-3) to 0.5 kmol.m(-3)) and extractant (tri-n-butyl phosphate, TBP) (0.36 kmol.m(-3) to 2.56 kmol.m(-3)) in different diluents (n-heptane, toluene, and methyl-iso-butyl ketone, MIBK). Different physiochemical properties such as dipole moment and ET parameter have been used for comparison. Results are given in terms of various parameters such as distribution coefficient, equilibrium complexation constant, loading ratio and extraction efficiency. Using expressions derived for extraction equilibria, equilibrium complexation constants (KE) were evaluated to be 0.369 m(3).kmol(-1), 0.482 m(3).kmol(-1), and 0.578 m(3).kmol(-1) for n-heptane, toluene, and MIBK, respectively, whereas solvation number of TBP (m) was estimated to be one for all the three diluents. Only (1:1) complex was proposed for all the three diluents with no overloading (Z < 0.5) in any case. Higher chemical extraction was observed in inactive diluents: n-heptane and toluene.