Abstract To alleviate the severe restacking of multilayer MXene nanosheets induced by strong van der Waals interaction, Ti3C2 MXene synthesized via SnCl2-assisted etching was employed as the precursor, and the effects of different intercalants on its microstructure and electrochemical performance were systematically investigated. Dimethyl sulfoxide (DMSO), tetrabutylammonium hydroxide (TBAOH), and tetramethylammonium hydroxide (TMAOH) were used as intercalants with varying reaction times. The results indicate that the intercalated samples exhibit considerably improved electrochemical performance in 6 M KOH electrolyte. Notably, the sample treated with TBAOH for 5 h (denoted as TB5) delivers the highest specific capacitance of 283.34 F g−1 at 0.5 A g−1. Furthermore, the cyclic voltammetry curves retain a quasi-rectangular shape at different scan rates, indicating excellent rate capability. This work provides an effective strategy for structural regulation of MXene-based electrode materials toward high-performance energy storage applications.