Self-supported polymer films were fabricated by the thiol-ene click cross-linking reaction in this work. The cross-linked frameworks were used to guarantee the stability the films. The hydrophilic monomer with different contents were introduced into the self-supported thick films and uniformly dispersed in the polymer frameworks. The interdigitated electrodes were screen printed with silver paste on the self-supported films to obtain humidity sensors. Herein, the self-supported film acts as both the sensor substrate and the humidity-sensing material. The humidity sensing performances of the obtained sensors were systematically researched. By optimizing the ratio of hydrophilic monomer in the polymer films, the sensitivities of the sensors were enhanced from 1.58 to 103.75 (in the humidity from 11% RH to 95% RH), the response under low RH environment was significantly improved with good linearity. The response/recovery times of the sensor within the humidity range are measured to be 12.5 s and hundreds of seconds. The prepared flexible sensors possess certain mechanical properties, and exhibit good stability under bending and long-term tests up to 60 days. The applications of the as-prepared sensor in the detection of non-contact human skin humidity, human respiration and relative humidity of green plant were explored. The sensor shows excellent sensing performance in various applications and indicates the potential application in wearable and multifunctional devices.