Abstract MXenes derived from 413 MAX phases are rarely studied but they have the potential to have superior electrical and mechanical properties thanks to a thicker monolayer (four layers of transition metal and three layers of carbon or nitrogen). In this paper, Nb 4 C 3 T x MXene nanosheets are delaminated and freestanding film with 1.77 nm interlayer spacing is obtained, which is larger than that of most previous MXenes. When Nb 4 C 3 T x freestanding films are tested as supercapacitors electrodes, Nb 4 C 3 T x shows high volumetric capacitance, 1075, 687, and 506 F cm −3 in 1 m H 2 SO 4 , 1 m KOH, and 1 m MgSO 4 , respectively, at the scan rate of 5 mV s −1 . An in situ X‐ray diffraction technique is used to study the structural changes during the electrochemical charging in 1 m H 2 SO 4 and 1 m MgSO 4 . There is almost no change in the 21 Å interlayer spacing during the cycling, because the space between the MXene layers is sufficient to accommodate the insertion and deinsertion of cations. This can lead to stable performance of Nb 4 C 3 T x MXene energy storage devices.