A new set of hybrid poly(ether-arylidene-ether-sulphone)s containing diarylidenecycloalkanone moieties in the polymers main chains has been synthesized in good yields by solution poly-condensation well known polymerization method. The chemical structures of all precursors, monomers and model compound were confirmed by both elemental and spectral data. More particularly, a modified electrode of Co +2 cationic sensor was prepared by the coating of a glassy carbon electrode with synthesized copolymer 8 e as a thin layer. The fabricated cationic sensor was displayed long-term stability, enhanced electrochemical activity, good sensitivity, shorter response time, broad linear dynamic range and lower detection limit. A calibration curve is plotted as current versus concentration of Co +2 ions. The cationic sensor sensitivity is calculated from the slope of calibration curve as 12.8165 µA nM −1 cm −2. The detection limit (0.74 ± 0.04 nM) is also estimated from the signal to noise ratio of 3. Therefore, the development of Co +2 cationic sensor might be a novel effort with hybrid sulphone polymers by electrochemical method to ensure the sustainability in health care sector.