As-grown n-4H-SiC/SiO2 capacitors exhibit anomalous capacitance-vs.-voltage (C–V) characteristics at low temperatures. Abrupt minima appear in the C–V curves at specific values of the gate voltages independent of the sample temperature, strongly suggesting the presence of resonant electron tunneling. We put forward a qualitative model where neutral donor states present at the SiC/SiO2 interface enable electron tunneling into distinct energy levels in the oxide. Numerical simulations based on this model show close agreement with the anomalous C–V characteristics observed experimentally. The model implies that under given conditions, i.e., the existence of a sufficient density of neutral donors at the semiconductor/oxide interface and empty electron states in the oxide layer, abrupt minima are in general to be expected during C–V measurements of metal-oxide-semiconductor capacitors.