Ionic covalent organic frameworks (ICOFs) have recently emerged as promising candidates for solid-state electrolytes. Herein, we report the first example of a series of crystalline imidazolate-containing ICOFs as single-ion conducting COF solid electrolyte materials, where lithium cations freely travel through the intrinsic channels with outstanding ion conductivity (up to 7.2 X 10(-3) S cm(-1)) and impressively low activation energy (as low as 0.10 eV). These properties are attributed to the weak Li ion- imidazolate binding interactions and well-defined porous 2D framework structures of such ICOFs. We also investigated the structure-property relationship by varying the electronic properties of substituents (electron donating/withdrawing) that covalently attached to the imidazolate groups. We found electron withdrawing substituents significantly improve the ion-conducting ability of imidazolate-ICOF by weakening ion-pair interactions. Our study provides a convenient bottom-up approach toward a novel class of highly efficient single-ion conducting ICOFs which could be used in all solid-state electrolytic devices.