MXene Titanium Carbide has attracted extensive attention in the application fields of energy storage devices such as supercapacitors. However, most scholars study multi-layer MXene Ti3C2 and its composite. In particular, the effect of few-layer Ti3C2 on electrochemical performance and the charge storage mechanism in the process of energy storage still need to be further explored. To improve the specific capacitance, a microwave assisted hydrothermal technique was used to prepare few-layer Ti3C2. The microstructure of few-layer Ti3C2 was further analyzed by SEM and TEM. The dense Ti3AlC2 (0002) planes were bent and van der Waals bonds between the layers broken. The layers became more distorted under the joint action of etching agent and microwave hydrothermal solution, finally fractured and dissociated, forming few-layer Ti3C2. The mass specific capacitance of few-layer Ti3C2 is 418.07 F g−1, which is 102.63% higher than that of multi-layer Ti3C2. Through the kinetic analysis of the electrochemical energy storage processes, it was found that the charge storage of the few-layer Ti3C2 is mainly from the contribution of the surface capacitance. This provides a new direction for the simple and efficient synthesis of high specific mass capacitance MXene Ti3C2 as electrode material for supercapacitors.