Influence of thickness and growth condition of AlN spacer on electrical properties of AlGaN/AlN/GaN high-electron-mobility transistors (HEMTs) grown on 4-in. Si substrate was studied. Hall measurements show the mobility of AlGaN/AlN/GaN heterostructure varies with different thickness of AlN spacer and a narrow high-mobility window was obtained. The surface and structure studies indicate that both increasing growth temperature and lowering pressure benefit the quality of AlN and AlGaN, which leads to improvement of Hall mobility, except the temperature higher than that of GaN growth. Drain current–voltage (Ids–Vds) characteristics of such HEMTs exhibit the maximum current density (Imax) and tranconductance (gmax) have the similar trend with the mobility due to different interface roughness and piezoelectric field induced by part relaxation of tensile strain in AlGaN grown on AlN. The optimum properties of HEMT (Imax = 807 mA/mm, gmax = 221 mS/mm) are obtained when 1 nm AlN spacer grown at 1130 °C and 100 Torr.