The liquid–liquid equilibria of systems that involves lactic acid in the aqueous phase and tri-iso-octylamine with diluents as dodecane and 1-dodecanol (active or/and inert) were measured experimentally at three temperatures (306.15, 310.15, and 316.15 K). A previous liquid–liquid equilibrium model that is based on Nernst’s distribution law and mass action law equilibrium equations was extended and generalized for stoichiometric ratios (amine/acid) 1:n. The effect of the diluents and the tertiary amine on the liquid–liquid equilibrium is shown and quantified in terms of the predicted values of the distribution coefficient, chemical equilibrium constants, and temperature. The lactic acid concentration in equilibrium for the organic phase decreases as follows: water/LA/TiOA/1-dodecanol system > water/LA/TiOA/dodecane/1-dodecanol > system water/LA/TiOA/dodecane system.