Surface passivation process of GaN utilizing electron-cyclotron-resonance (ECR) excited plasma has been characterized and optimized for realization of stable operation in GaN-based high-power/high-frequancy electronic devices. From XPS analysis, the NH4OH treatment as well as the ECR-N2 and ECR-H2 plasma treatments were found to be effective in removing natural oxide and contaminants from the GaN surface. The SiNx/GaN structure prepared by the ECR excited plasma chemical vapor deposition (ECR-CVD) process showed better C-V behavior compared to the SiO2/GaN structure. Surface treatment process using the ECR plasma improved interface properties and achieved the Dit value of 21011 cm-2 eV-1 or less. An estimate of the valence band offset by XPS showed that the present SiNx/n-GaN structure has a type-I band lineup, suitable for the surface passivation of GaN-based devices. No pronounced stress remained at the SiNx/GaN interface, which was confirmed by Raman spectroscopy.