Sintered silver (Ag) die-attach has attracted much attention in power systems with high power density and high operating temperature. In this paper, we proposed a novel surface modification method for Ag nanoparticles with organic amines as a coating agent for enhancing the pressureless sintering performance. This work systematically introduced the Ag nanoparticle modification process, Ag paste preparation, and sintering process and compared the changes in the sintering performance of Ag nanoparticles after modification with four different alkyl chain lengths of amines. The study showed that the sintered films of Ag nanoparticle pastes modified with n-octylamine (NOA) can achieve the lowest resistivity of the sintered film and the highest shear strength of the bonded joints. The resistivity of the sintered Ag film is affected by the grain size and microscopic morphology, and the strength of the bonded joints is also related to the sintering density and the amount of organic residues. The thermal behavior of the Ag particles coated with different amines is measured by thermal analysis. Finally, the mechanism of NOA-modified Ag nanoparticles to improve the sintering performance is proposed. This study can provide effective data and theoretical support for the further promotion and application of nano-Ag pressureless sintering.