L-ascorbyl palmitate (L-AP) is a potential fat crystallization modifier, formed by the ester bond of ascorbic acid and palmitic acid. The effects of L-AP on the crystallization behavior of palm oil (PO) and its application in bread were systematically investigated. L-AP addition led to higher crystallization rate and lower induction time of nucleation with the increasing concentration from 1% to 5%. L-AP slightly affected the growth mechanism of PO, and they all showed the instantaneous nucleation and linear growth. Meanwhile, in presence of L-AP, a desirable β′ polymorphism and lower thickness of the nanoscale crystals were observed in the PO. Higher fractal dimension (Db) and smaller average particle size (D) were acquired by analyzing the polarized light microscope (PLM) pictures, which represented more ordered organization of the crystal lattice due to the interactions between triglycerides and L-AP. Furthermore, the specific volume increased and the baking decreased after adding L-AP according to the baking analysis. Bread made of PO with L-AP was satisfactory, showing higher cell density, smaller cell average area and lower hardness. In summary, L-AP had great potential to be a highly effective fat crystallization modifier and increased the compatibility of PO to be severed as the formulations of baking fat in the food industry.