Two donor–acceptor type tetrathiafulvalene (TTF)-based covalent organic frameworks (COFs) are investigated as electrodes for symmetric supercapacitors in different electrolytes, to understand the charge storage and dynamics in 2D COFs. Till-date, most COFs are investigated as Faradic redox pseudocapacitors in aqueous electrolytes. For the first time, it is tried to enhance the electrochemical performance and stability of pristine COF-based supercapacitors by operating them in the non-Faradaic electrochemically double layer capacitance region. It is found that the charge storage mechanism of ionic liquid (IL) electrolyte based supercapacitors is dependent on the micropore size and surface charge density of the donor–acceptor COFs. The surface charge density alters due to the different electron acceptor building blocks, which in turn influences the dense packing of the IL near its pore. The micropores induce pore confinement of IL in the COFs by partial breaking of coulomb ordering and rearranging it. The combination of these two factors enhance the charge storage in the highly microporous COFs. The density functional theory calculations support the same. At 1 A g−1, TTF-porphyrin COF provides capacitance of 42, 70, and 130 F g−1 in aqueous, organic, and IL electrolyte respectively. TTF-diamine COF shows a similar trend with 100 F g−1 capacitance in IL.