First, a detailed analysis of the electrolytes, binders and electrode composition used in reported COF cathode materials for LIBs was carried out (Table ). In most cases, LiPF 6 in ethylene carbonate (EC)/dimethyl carbonate (DMC) (1/1) or LiTFSI in 1,3-dioxolane (DOL)/1,2-dimethoxyethane (DME) were used as electrolyte, while PVdF was the most commonly used binder. We have chosen DAAQ-TFP-COF as a model COF active material for this comprehensive investigation because of: i) its relatively high theoretical capacity; ii) the high chemical stability of the β-ketoenamine linkages; iii) it can be easily obtained in large quantities; iv) interestingly, two independent research groups reported very different capacities (54 and 110 mAh g -1 ) when the bulk COF was used as a cathode in lithium half-cells. As previously reported, . The third electrolyte is a commercial 1 M LiPF 6 in EC/DEC, which is commonly used for electrochemical characterisation of inorganic materials. The fourth electrolyte is 1 M LiClO 4 in cyclic carbonate (GBL), known for its high anodic and thermal stability. We first compared the cycling stability of DAAQ-TFP-COF electrodes at the current density of 150 mA g -1 with the electrodes containing PVdF binder (Fig. and S8, ESI). Using LiPF 6 in EC/DEC (1/1) and LiClO 4 in γ-butyrolactone (GBL) as electrolytes, the worst performances were obtained showing capacity retention of ~58% and ~67%, respectively, after 100 cycles (Figs. 1a, S8 and Table , ESI). The capacity fading observed when using LiPF 6 in EC/DEC could be explained by undesired side reactions or higher solubility of the redox polymer in carbonate-based electrolytes. In this sense, some previous electrochemical studies on (poly)anthraquinone linear polymers reported a higher solubility of the discharged phases and attributed the low capacity retention in carbonate electrolytes to both higher dissolution and irreversibility of the redox process. In contrast, when LiTFSI in DOL/DME (1/1) was used as electrolyte the initial capacity was 118.0 mAh g -1 and a much better capacity retention (90%) was observed after 100 cycles (Table , ESI). The electrochemical performance was further improved by replacing DOL/DME with TEGDME solvent since the specific capacity was maintained at 118.3 mAh g -1 after 100 cycles.