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In this work, we systematically investigated the <i>N</i>_x bonding defects that induced high photoluminescence internal quantum efficiencies (PL IQEs) and very fast radiative recombination processes in amorphous silicon oxynitride (a-SiN_xO_y) systems. The luminescent N‒Si‒O bonding-related defect states were checked for the XPS, EPR, and temperature-dependent steady-state PL (TD-SSPL) properties. The PL IQEs were calculated from PL quantum yields through the principle of planar geometry optics, and then confirmed by the TD-SSPL properties. The radiative recombination rates [<i>k_r</i>(R)] were determined by combining the PL IQE values and ns-PL lifetimes obtained from time-resolved PL measurements. Both the PL IQE, exceeding 72%, and the fast <i>k_r</i>(R) (~10⁸ s^&#8722;1) are proportional to the concentration of <i>N_x</i> defects, which can be explained by N‒Si‒O bonding states related to the quasi-three-level model, suggesting the possible realization of stimulated light emission in a-SiN_xO_y systems.