The reactive extractions of acetic acid, HAc, with tri-n-octylamine (TOA), Q, dissolved in three solvents with different dielectric constants (dichloromethane, butyl acetate, and n-heptane) without and with 1-octanol as phase modifier have been comparatively analyzed. The results indicated that the mechanism of the interfacial reaction between acid and extractant is controlled by the organic phase polarity. In absence of 1-octanol, the structures of the extracted complexes are HAc.Q for dichloromethane, HAc.Q 2 for butyl acetate, and (HAc) 2 Q 4 for n-heptane. These structures are modified by adding 1-octanol and become HAc.Q for extraction in dichloromethane or butyl acetate and (HAc) 2 Q 2 for extraction in n-heptane, respectively. Although the presence of 1-octanol improves the extraction efficiency, it leads to the reduction of extraction constants for lower-polar solvents, influence that is more significant for n-heptane.