AbstractThe melting properties and polymorphic behavior of binary and ternary blends of cocoa butter substitutes (CBS), cocoa butter (CB), and milk fat (MF) were studied by using pulsed nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), and X‐ray diffractometry (XRD). Hydrogenated palm kernel stearin (HPKS) and hydrogenated palm kernel olein (HPKO) were chosen as the two CBS feedstock fats. Both CBS/CB binary blends displayed significant eutectic behaviors. Multiple melting peaks and eutectic effects were observed at 30–50% addition levels of CB to HPKS. The range was broader in HPKO/CB blends. Dilution effect was observed in both CBS/MF blends while slight monotectic effect was also observed in HPKO/MF blends. Ternary phase diagrams and melting curves showed that eutectic effects existed in both ternary blends and the degree of interaction depended on the content of CB and MF. XRD results showed that when pure fat component in each blend exceeded 80%, its polymorphism dominated in the ternary blends. However, when CBS/CB or MF /CB were added at a comparative content (blends D and F), both β and β′ form existed.Practical applications: Phase properties of fat blends may have significant effects on the sensory characteristics and physical properties of the final products, such as hardness, brittleness, and the bloom formation. This study evaluates the melting properties and the polymorphic characteristics of fat blends of constituents with potential use in the manufacture of confectionery products. A comprehensive analysis of binary and ternary fat blends was conducted in order to provide a guide for compound chocolate production formulation.