Humidity sensing and water molecule monitoring have become hot research topics attributed to their potential applications in monitoring breathing/physiological conditions of humans, air conditioning in greenhouses, and soil moisture in agriculture. However, there is a huge challenge for highly sensitive and precision humidity detection with wireless and fast responsive capabilities. In this work, a hybrid/synergistic strategy was proposed using a LiNbO3/SiO2/SiC heterostructure to generate shear-horizontal (SH) surface acoustic waves (SAWs) and using a nanocomposite of polyethylenimine-silicon dioxide nanoparticles (PEI-SiO2 NPs) to form a sensitive layer, thus achieving an ultrahigh sensitivity of SAW humidity sensors. Ultrahigh frequencies (1∼15 GHz) of SAW devices were obtained on a high-velocity heterostructure of LiNbO3/SiO2/SiC. Among the multimodal wave modes, we selected SH waves for humidity sensing and achieved a high mass-sensitivity of 5383 MHz · mm2 · μg–1. With the PEI-SiO2 NP composite as the sensitive layer, an ultrahigh sensitivity of 2.02 MHz/% RH was obtained, which is two orders of magnitude higher than those of the conventional SAW humidity sensors (∼202.5 MHz frequency) within a humidity range of 20–80% RH.