Due to the mutual repulsion between their hydrophilic surface terminations and the high surface energy facilitating their random restacking, 2D MXene nanosheets usually cannot self-assemble into 3D macroscopic gels with various applications in the absence of proper linking agents. In this work, a rapid spontaneous gelation of Ti₃C₂T_x MXene with a very low dispersion concentration of 0.5 mg mL⁻¹ into multifunctional architectures under moderate centrifugation is illustrated. The as-prepared MXene gels exhibit reconfigurable internal structures and tunable rheological, tribological, electrochemical, infrared-emissive and photothermal-conversion properties based on the pH-induced changes in the surface chemistry of Ti₃C₂T_x nanosheets. By adopting a gel with optimized pH value, high lubrication, exceptional specific capacitances (~ 635 and ~ 408 F g⁻¹ at 5 and 100 mV s⁻¹, respectively), long-term capacitance retention (~ 96.7% after 10,000 cycles) and high-precision screen- or extrusion-printing into different high-resolution anticounterfeiting patterns can be achieved, thus displaying extensive potential applications in the fields of semi-solid lubrication, controllable devices, supercapacitors, information encryption and infrared camouflaging.