The interfaces between high-κ dielectrics, grown by atomic layer deposition, and semiconductors have been characterized using various electrically detected magnetic resonance spectroscopy techniques. The dominant center at the interface was found to be Pb0-like. Microwave contactless photoconductive resonance and defect-assisted spin dependent tunneling spectroscopies, performed at low temperatures, reveal also a signal which could be related to E’-like near interfacial oxide traps.