A titration microcalorimeter with the sample cells of 1 mL and 3 mL volume was constructed by combining LKB-2107 ampule microcalorimeter with an improved Thermometric titration microcalorimeter. Its sensitivity and precision were tested with the baseline noise and stability, the measurement of energy equivalent, and the linear relation of electric energy and integral area as the function of voltage (V )-time (t ). Its accuracy was demonstrated by measuring the dilution enthalpy of a concentrated sucrose solution and the micelle-forming enthalpy of sodium dodecyl sulfate (SDS) in aqueous solution respectively. At the same time, the enthalpy of interaction between SDS and didodecyldimethylammonium bromide (DDAB) was measured by using the titration microcalorimeter, and the phase behavior of SDS-DDAB aqueous mixture was discussed. The microcalorimetric results show that the enthalpy of interaction between SDS and DDAB micelles is ?29.53 kJ/mol, the enthalpy of formation of 1:1 SDS-DDAB salt is ?125.8 kJ/mol, the vesicle-forming enthalpy of SDS-DDAB is 41.23 kJ/mol, and the enthalpy of phase transition from vesicles to SDS rich micelle is 32.10 kJ/mol.