Recently, AlN plasma-enhanced atomic layer deposition (ALD) passivation technique had been proposed and investigated for suppressing the dynamic on-resistance degradation behavior of high-electron-mobility transistors (HEMTs). In this paper, a novel gate dielectric and passivation technique for GaN-on-Si AlGaN/GaN metal-insulator-semiconductor high-electron-mobility transistors (MISHEMTs) is presented. This technique features the AlN thin film grown by thermal ALD at 400°C without plasma enhancement. A 10.6-nm AlN thin film was grown upon the surface of the HEMT serving as the gate dielectric under the gate electrode and as the passivation layer in the access region at the same time. The MISHEMTs with thermal ALD AlN exhibit enhanced on/off ratio, reduced channel sheet resistance, reduction of gate leakage by three orders of magnitude at a bias of 4 V, reduced threshold voltage hysteresis of 60 mV, and suppressed current collapse degradation.