New polyelectrolytes derived from ionene-containing photocurable reactive oligomer (PIDM) were prepared for water-resistant humidity-sensitive membranes. The mixture of PIDM, hexamethylene dimethacrylate (HDM), pentaerythritol triacrylate dimer (SP1013), and photoinitiator was simultaneously coated on the sensor electrode with photoinitiated radical polymerization. The pretreatment of the substrates with vinyl-type silane-coupling reagent was performed for improving the water durability and stability of the sensors at high temperature and humidity. When the resistance dependences on the relative humidity of the crosslinked PIDMs were measured, it was found that the resistance varied three orders of magnitude between 20 and 90%RH, which was required for the humidity sensor operating at ambient humidity. Their hysteresis, temperature dependence, response time, water durability, and high temperature/humidity stabilities were measured and evaluated as a humidity-sensing membrane.