Silver nanoparticle (NP) inks have been widely used in the ink-jet printing field because of their excellent properties during low-temperature sintering. However, the organic dispersant used to prevent the aggregation and sedimentation of NPs can hinder the sintering process and result in the high resistivity of sintered films. In this study, silver thin films derived from silver NP ink with polyvinylpyrrolidone (PVP) dispersant were sintered in different atmospheres of pure nitrogen, air, and pure oxygen. The effect of the oxygen content in the sintering atmosphere on the thermal properties of the ink, the electrical resistivity and microstructure of the sintered films, and the amount of organic residue were studied by using differential scanning calorimetry, the four-point probe method, scanning electron microscopy, Fourier transform infrared spectroscopy, etc. The mechanism of optimizing the film resistivity by influencing the decomposition of the PVP dispersant and the microstructure evolution of the silver thin films through the sintering atmosphere was discussed. The results demonstrated that an oxygen-containing atmosphere could be effective for silver NPs in two ways. First, the oxygen content could enhance the diffusion ability of silver atoms, thus accelerating the stage transition of microstructural evolution at low temperatures. Second, the oxygen content could enable the PVP to decompose at a temperature much lower than in conditions of pure nitrogen, thus helping to finalize the densification of a silver film with a low resistivity of 2.47 μΩ·cm, which is approximately 1.5-fold that of bulk silver. Our findings could serve as a foundation for the subsequent establishment of ink-jet printing equipment and the optimization of the sintering process for printing silver patterns on flexible substrates.