Microstructural investigation of palm oil (PO) containing 8% monopalmitin (MP) was performed using synchrotron radiation microbeam (beam area of 5 脳 5 渭m2) X-ray diffraction (SR-渭-XRD). The blend was isothermally crystallized at 20 掳C and analyzed shortly after reaching the crystallization temperature and after aging at 20 掳C. The SR-渭-XRD technique allowed demonstration of the template effect of the monoacylglycerol (MAG) by showing that the PO crystals were orientated by the previously crystallized MP. Interactions through the palmitic acid moiety in PO and MP must have played decisive roles in this template effect as palmitic acid is a major fatty acid in PO. Analysis of aged samples revealed that the MP crystals migrate and concentrate into large spherulitic crystals during long-term storage, probably caused by a process of Ostwald ripening.