Novel electrode materials are always explored to achieve better performance of supercapacitors. Titanium carbide MXenes, Ti3C2Tx, are one of the very promising candidates for electrode materials in supercapacitors due to their unique structural and ion storage properties as 2D materials. Their large specific surface area, adjustable functionalized surface terminals, high electrical conductivities, hydrophilicity, and high Faradaic capacitance, also known widely but confusingly as pseudocapacitance, are highly desirable for making high‐performance electrodes with increased dis‐/charging rates and capacities. Herein, some selective electrochemical considerations of Ti3C2Tx MXenes for uses in supercapacitors are critically reviewed and assessed, aiming at a better fundamental understanding of the electrochemical basics and processes in Ti3C2Tx MXene‐based electrode materials for supercapacitor applications.