New polyelectrolytes derived from poly(amide-sulfone)s and 1,5-dibromopentane were simultaneously fabricated on the electrode by the crosslinking reaction. The substrate was pretreated with a bromoalkyl-containing, silane-coupling agent to anchor the humidity-sensitive membrane to the substrate through the covalent bond. When the resistance dependence on the relative humidity of the crosslinked poly(amide-sulfone)s was measured, the resistance varied by three orders of magnitude between 20%RH and 90%RH, which was the required RH range for a humidity sensor operating at ambient humidity. Their water durability, long-term stabilities under various environments, hysteresis and response and recovery times were measured and evaluated as a humidity-sensing membrane.