We investigated the high absolute photoluminescence quantum yields (PL QYs) from tunable luminescent amorphous silicon oxynitride (a-SiNxOy) films. The PL QY of 8.38 percent has been achieved at PL peak energy of 2.55 eV in a-SiNxOy systems, which is higher than those of reported nanocrystal-Si embedded silicon nitride films. The existence of N-Si-O bonding states was confirmed by performing FTIR, XPS and EPR measurements. The PL QY is proportional to the concentration of Nx defects, indicating the dominant contribution of luminescent N-Si-O bonding states in radiative recombination processes. Particularly, we precisely monitored the ns-PL lifetimes evolution profile versus detected emission wavelengths, and further verified that the N-Si-O bonding states are responsible for highly efficient PL.