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This article presents a facile synthesis method used to obtain new composite films based on polylactic acid and micro-structured hydroxyapatite particles. The composite films were synthesized starting from a polymeric solution in chloroform (12 wt.%) in which various concentrations of hydroxyapatite (1, 2, and 4 wt.% related to polymer) were homogenously dispersed using ultrasonication followed by solvent evaporation. The synthesized composite films were morphologically (through SEM and atomic force microscopy (AFM)) and structurally (through FT-IR and Raman spectroscopy) characterized. The thermal behavior of the composite films was also determined. The SEM and AFM analyses showed the presence of micro-structured hydroxyapatite particles in the film’s structure, as well as changes in the surface morphology. There was a significant decrease in the crystallinity of the composite films compared to the pure polymer, this being explained by a decrease in the arrangement of the polymer chains and a concurrent increase in the degree of their clutter. The presence of hydroxyapatite crystals did not have a significant influence on the degradation temperature of the composite film.