Despite their finite spatial extent, interfaces can have profound impacts on microstructure properties. This is because of their distinct phase-like properties distinguishing them from the adjacent homogeneous bulk structure. When noticed by solute atoms, interfaces can experience their own chemical phase changes. In this talk, we investigate the constrained states of chemically decomposed phases at interfaces. A density-based theory of interfaces is proposed to describe the confined chemical decomposition at general grain boundaries. Here the grain boundary is viewed as a lesser dense, defected structure with reference to the corresponding bulk structure. Using this picture, the thermodynamic origins of interfacial spinodal phenomena are revealed. We also show that transient interfacial spinodals can be activated over a large alloy composition range, enabling kinetic engineering of interfacial chemistry.