Al2O3 films have been deposited on n-type and p-type 4H‐SiC by atomic layer chemical vapor deposition using trimethylaluminum as a precursor for aluminum and both H2O and O3 as an oxidant. After oxide deposition, annealing at different temperatures (800, 900, 1000°C) in argon atmosphere for different durations (1, 2, 3h) was performed. Bulk and interface properties of the oxide films were studied by capacitance-voltage, current-voltage, deep level transient spectroscopy, and thermally dielectric relaxation current (TDRC) measurements. The results reveal a decreasing flatband voltage with increasing annealing time, suggesting decrease of oxide charges and deep interface traps. After 3h annealing at 1000°C of the n-type samples, the flatband voltage is reduced to 6V compared to a value in excess of 40V for as-deposited samples. The TDRC measurements on annealed Al2O3∕SiC (n-type) capacitors …