This paper presents the laboratory results of extraction of formic acid from the reaction of sodium formate with carbon dioxide : HCOONa(w) + CO2(g) + H2O(w) + Am(o) reversible arrow NaHCO3(s,w) + HCOOHAm(o). The reaction was operated at room temperature. Sodium formate (aqueous solution) was reacting with carbon dioxide in the presence of organic tertiary amine. The reaction can be divided into two steps : HCOONa(w) + CO2(g) + H2O(w) reversible arrow NaHCO3(s,w) + HCOOH(w) (1); HCOOH(w) + Am(o) reversible arrow HCOOHAm(o) (2). In the first step, sodium bicarbonate and formic acid were formed. Produced formic acid was immediately extracted into an organic phase by tertiary amine as expressed in step two. When proper diluents were used, solid sodium bicarbonate occurred in an aqueous phase. The experimental investigation showed that temperature, pressure, and concentration of sodium formate affected extraction equilibrium. But diluents and their ratio with tertiary amine affected extraction equilibrium significantly. It was found that the solvation of formed complex HCOOHAm(o) in diluents has a great influence on the extraction of formic acid by tertiary amine. The high polarity of the diluent and the low solvophobic property of the diluent with tertiary amine are beneficial to the extraction of formic acid.