SummaryCocoa butter is the most important ingredient of chocolate, which determines its melting behaviour. Variations in the melting characteristics of cocoa butter can profoundly affect the performance and suitability for their industrial utilisation. Over time, researchers have been attempting to establish a logical relationship between cocoa butter's unique thermal properties and the amount of saturated to unsaturated fatty acids in mono, di and triglycerides, and fatty acids (as major components), and free fatty acids, soap, primary oxidation products, minerals, moisture, phospholipids, tocopherols, unsaponifiable matters and metals (as minor components) found in cocoa butter. In this research, the thermal behaviours of thirteen samples of cocoa butter with different origins were investigated using isothermal differential scanning calorimetry. The cocoa butters starting temperature of crystallisation, temperature of maximum heat release, temperature of completed crystallisation and the enthalpy of heat release during recrystallisation were evaluated. In addition, the chemical composition (moisture, acidity, peroxide, minerals and soap content), fatty acid and triacylglycerol composition were used to establish an MLP‐ANN with fourteen input neurons connected by two flexible, sigmoid activation function layers. The back‐propagation was used to train the artificial neural network (ANN) structure and optimise the error of prediction. The study showed that the MLP algorithm can predict the thermal behaviour of CB samples with trace error, regardless of plant growth and extract process condition.