A porous organic polymer (POP) has been developed for dual-ion storage in all organic symmetric rechargeable batteries. The triphenylamine-pyrene-based POP could host sodium and hexafluorophosphate ions acting as the anode and the cathode, respectively, through the adsorption-intercalation and insertion mechanism. The current study highlights the concept of widening the potential window of a dual ion battery by judicious selection of the constituent moieties.