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Due to thetrade-offeffect between the high water adsorption and low stability under high Relative Humidity of polymer matrix, fabrication of resistive-type polymer-based humidity sensors with a wide impedance response and excellent stability in high relative humidity remains a great challenge. Aim at solving that, a novel polymeric humidity sensing matrix, specifically a tadpole-shaped, polyhedral oligomeric silsesquioxane (POSS) containing block copolymers (BCPs) of POSS-poly(methyl methacry-late)-polystyrene (POSS-PMMA-SPS) were proposed. This novel BCP was synthesized using atom transfer radical polymerization (ATRP) employing a two-step approach, and following post sulfonation, a series of sulfonated BCPs (POSS-PMMA-SPS) with different sulfonation degree was obtained. The subject humidity sensors were produced using different sulfonated BCPs employing a dip-coating technique, and three wide-impedance response humidity sensors were produced. Each of these sensors exhibited an excellent humidity-sensing response of more than 104 within the humidity range from 11%to 95%RH. In particular, the humidity sensor S-6 that had a proper degree of sulfonation presented a relatively fast response (t90%of 11 s and 80 s in both the water adsorption and desorption processes), and superior repeatability for more than 30 days.