Low-temperature bonding (≤300 o C) using Ag nanoparticles (Ag NPs) is considered to be the new generation of bonding technology in power electronics. The oxygen-accelerated sintering has been observed by many researchers which is attributed to the decomposition of organics covered on Ag NPs. In this work, organic-free Ag NPs are fabricated to eliminate the influence of organics, and it is found that the accelerated bonding process by oxygen is strongly correlated to the self-confined amorphous Ag-O compound shell on the surface of Ag NPs. In experiments, the sintering process is apparently accelerated by the elevating oxygen content, and the amorphous shell is observed after sintering, which do not grow thicker even in pure oxygen ambient for a long time while performing active chemical evolutions. In simulations, the results match well with the experiments and indicate that the amorphous shell performed the dynamic oxidation and decomposition process. This dynamic equilibrium is caused by the instability of silver oxides, which would enable the amorphous shell to activate the mobility of the surface mass flow and promote the surface diffusion. The shear strength of SiC chip increased by 354% when bonding in pure oxygen, targeting a broad variety of applications in electronic packaging.