Two types of Schottky structure sensors (silicon nanowire (SiNW)/ZnO/reduced graphene oxide (rGO) and SiNW/TiO2/rGO) were designed, their humidity resistance characteristics were studied, and the sensors were applied to detect sleep apnea through breath humidity monitoring. The results show that the resistance of the sensors exhibited significant changes with increasing humidity, the response times of the two sensors within the relative humidity range of 23–97% were 49 s and 67 s, and the recovery times were 24 s and 43 s, respectively. Meanwhile, continuous breathing monitoring results indicate that the sensitivity of the sensors remained basically unchanged during 10 min of normal breathing and simulated apnea. The response of the sensor is still good after 30 days of use. We believe that the Schottky structure composite sensor is a very promising technology for human breathing monitoring.