The kinetic phase behavior and phase transformation paths of tripalmitoylglycerol (PPP) and 1,3‐dipalmitoyl‐2‐stearoyl‐sn‐glycerol (PSP) mixtures are investigated at 10.0 °C min−1 (fast cooling) and 1.0 °C min−1 (slow cooling) cooling rates, and re‐heating at 5.0 and 1.0 °C min−1. Mixtures with 0.1 XPSP increments are studied in terms of polymorphism, crystallization, and melting. At the higher cooling rate, all samples crystallized in the α polymorph, while at the lower cooling rate, samples containing XPSP ≤ 0.3 crystallized in the α polymorph and samples containing XPSP > 0.3 crystallized in the β′ polymorph. During heating, all samples transformed to a more stable β′ form and melted finally in the β form (XPSP ≤ 0.3) or in the β′ form (XPSP > 0.3). Kinetic phase diagrams are determined from the DSC heating thermograms and XRD patterns obtained during cooling and heating and displayed an eutectic behavior with an eutectic point at XPSP = 0.3 irrespective of the rate at which the samples are cooled and re‐heated. The eutectic temperature is independent of the cooling and heating rates used. This study shows that PSP has a strong effect on the physical properties of PPP–PSP mixtures and dominates a large part of the phase behavior of the PPP–PSP binary system. At lower PSP concentration, the mixtures transform to the most stable β form, but at increasing PSP concentration the mixtures stabilize in the β′‐phase which is preferred in many food application because this results in a smooth texture. Practical Application: The results of this study are useful for the food industry as they can help in understanding the functionality of hard fat‐based structuring agents in end applications and in developing new triacylglycerol‐based crystallization and structuring agent for specific food applications PPP–PSP mixtures, either cooled or heated at lower or higher rate, all samples display different type of phase behavior: α‐ to β′‐phase development via recrystallization from the melt for mixtures having low PSP concentration, an α‐ to β′‐phase development via solid–solid transformation, a β′2‐ to β′1‐phase development via solid–solid transformation, and a β′‐ to β‐phase development via solid–solid transformation with an apparently typical eutectic behavior, with an eutectic concentration (XE) of about XPSP = 0.3. The eutectic temperature is not affected by the processing conditions applied. In the XPSP ≤ XE side of the phase diagram, the transition is different, being more β stable and is strongly affected by increasing PSP content (XPSP > XE side), which are more β′ stable. [ABSTRACT FROM AUTHOR]