In the present study electrostatically‐driven pH responsive supramolecular, self‐assembled hydrogels of the trilacunary Wells‐Dawson‐type 15‐tungsto‐2‐phosphate polyanion [P2W15O56]12− (P2W15) and polyethyleneimine were prepared. Crosslinking was achieved through electrostatic interactions between cationic polyethyleneimine and P2W15. The pH responsiveness was induced by acrylic acid. Benzoyl peroxide was used as an initiator, for initiating the polymerization reaction, anchoring polyacrylic acid on the polyethyleneimine skeleton. The prepared sea‐green color hydrogels were characterized by FT‐IR, SEM, XRD and thermal analysis (TGA‐DSC). The swelling index, P2W15 release studies and pH responsive properties of the developed supramolecular hydrogels were evaluated at pH 1.2 and 7.4, showing maximum swellability and release characteristics at pH 7.4. For determining the P2W15 release mechanism different mathematical models such as zero order, first order, Higuchi model and Krosmeyer‐Peppas models were applied and the results showed that embedded P2W15 release follows zero‐order kinetics. The cytotoxicity results showed that naked and embedded P2W15 exhibited dose‐dependent cytotoxicity against cancer cell lines (MCF‐7; Hela) with minimal effects on normal cells (Vero). The hydrogels developed through electrostatic interactions exhibited desirable qualities of a drug delivery system that can be used for the delivery of the embedded polyanion.