MOFs stand out due to their various chemical compositions and well-defined crystalline structures acting as templates in the formation of precisely engineered pore architectures, enabling the production of carbon materials with uniform porosity and high surface areas. Remarkably, MOFderived porous carbons show high application potential as supercapacitors and Zn-ion capacitors, since they can achieve high capacitance, cycling performance and rate stability. For example, ZIF-8 and Ni(terephthalate) materials were used as precursors for porous carbons via pyrolysis, resulting in promising materials for aqueous Zn-ion capacitors showing maximum specific capacitance values of 314 F g -1 (at 0.5 A g -1 ) and 123 F g -1 (at 0.2 A g -1 ), respectively and BET surfaces of 270 m 2 /g and 551 m 2 /g, respectively . Similarly, MIL-47 was pyrolyzed yielding carbon material with 2125 m 2 /g BET surface, which showed good performance as both symmetric supercapacitor (326 F g -1 at 0.5 A g -1 ) and Zn-ion capacitor (289.2 F g -1 at 0.2 A g -1 ). We would like to emphasize that alkali metal hydroxides, carbonates and other salts have widely been applied as activation agents in the preparation of porous carbons from organic precursors, due to the ability of alkali cations to facilitate the high-temperature chemical etching of carbon, and mediate the formation of materials with controlled porosity and morphology. For similar reasons, molecular organic salts of alkali metals have been used as precursors in the selftemplating strategy involving pyrolysis of the precursor followed by the removal of inorganic residues in order to achieve highly porous carbons. Nevertheless, in comparison to the transition-metal based networks the alkali metal-based coordination networks remain vastly unexplored as self-templating precursors of porous carbon materials, represented by only a handful of papers. This might be related to the scarcity of the s-block metal-based coordination polymers in comparison to the transition metal-based systems. Moreover, the alkali-based coordination networks are more flexible and potentially highly adaptive, but also more difficult to predesign, due to multitude of possible coordination geometries of the underlying metal centres. In general, the final properties and functionalities of carbon materials are determined by both conditions of the carbonization process and the nature of precursors. Herein, in the course of our ongoing efforts towards development of functional 0D molecular systems as well as 1D, 2D, 3D coordination polymers and other hybrid organic-inorganic materials for energyrelated applications, we report on a simple and green approach to the synthesis of new alkali metal-based coordination networks, showing promising potential as self-templating precursors for porous carbon materials (Figure ). A series of 2D and 3D Li + , Na + , K + -based coordination networks involving 1,3,5-benzenetricarboxylate (BTC) linkers was prepared in multigram scale under mild conditions and structurally well-characterized. Then the resulting alkali-BTC coordination polymers were applied as sacrificial templates for porous carbons via thermolysis, yielding carbon materials of diverse porosity depending on the precursor type, which aims to combine the advantages of both coordination networks and alkali salts in the pyrolytic approach to formation of functional porous carbons Moreover, the developed porous carbons with BET surface areas in the range of 961 -1871 m 2 /g were examined as supercapacitors, showing promising specific capacitance values in the range of 163.2 -213.4 F g -1 (at 0.1 A g -1 ). In this vein, the carbon carbons were tested as Zn-ion capacitors (AZICs), which revealed remarkable specific capacities up to 754.7 F g -1 at 0.1 A g -1 for the carbon material prepared using the potassium coordination network as a precursor. As suggested by the conducted analyses, the electrochemical performance of the developed carbon materials was related to the type of the internal porous structure determined by the employed alkali metal-based coordination network precursors.