The internal standard (IS) CE (IS-CE) method is an interesting alternative to other methods for the determination of acidity constants of compounds. Although some of the advantages of this method have been already reported, the method has not been tested yet as regards to temperature effects. This has been the aim of this work, where it is demonstrated that the method can be applied successfully for the determination of pK(a)s at different temperatures, if the acidity constant of the IS at the desired temperature is known. The fact of obtaining the acidity constants at different temperatures allows the calculation of some thermodynamic quantities, such as the molar standard enthalpy and the molar standard entropy in a fast way. It is also demonstrated that if the IS and the test compound have similar standard enthalpy increment, the IS compensates uncontrolled possible temperature fluctuations (e. g., due to Joule heat) inside the capillary obtaining reliable acidity constant values at the desired temperature.