The Ag-Ni alloy has high electrical conductivity, good thermal conductivity, high specific heat capacity, and excellent electrical wear resistance if the Ni-rich phase is dispersedly distributed in the Ag-based matrix. It has been widely used in the medium load contactors, magnetic starters, relays, etc. However, Ag-Ni alloy is a typical monotectic system. Generally, the liquid-liquid phase transformation leads to the formation of a solidification microstructure with serious phase segregation. So far, there have been few studies on the solidification process of Ag-Ni alloys and powder-metallurgical techniques are commonly used to prepare Ag-Ni alloys in industry. In this work, casting experiments and microhardness test were carried out with the Ag-Ni monotectic alloy. The samples with composite microstructure, in which the Ni-rich particles dispersed homogeneously in Ag matrix, were obtained. The microhardness of Ag-Ni alloy increases with the increase of nickel content and the cooling rate of the sample during solidification. When the cooling rate during the liquid-liquid phase transition of the Ag-4.0%Ni alloy reaches 1800 K/s, the microhardness of the Ag-4.0%Ni alloy is close to that of the Ag-10.0%Ni sheet electrical contacts produced by powder metallurgy. A model describing the microstructure evolution during cooling Ag-Ni monotectic alloy melt has been proposed. The process of microstructure formation has been simulated and discussed in details. The results indicate that the cooling rate during the nucleation of the Ni-rich droplets/particles has a dominant influence on the solidification microstructure. The average radius of the Ni-rich particles increases with the increase of nickel content, while it decreases with the increase of the cooling rate during solidification. The average radius of the Ni-rich particles shows an inverse square root dependence on the cooling rate during the nucleation of the Ni-rich droplets/particles. The Ostwald coarsening of the Ni-rich droplets/particles is very weak during cooling Ag-Ni monotectic alloy melt. Rapid/sub-rapid solidification has a good application prospect in the preparation of the high-performance Ag-Ni contact materials.