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Differential scanning calorimetry was used to study the temperatures and character of phase transitions of fibers based on polyether ether ketones. It is shown that in the production of fine fibers from polyether ether ketones, a predominantly amorphous structure is formed. Increasing the temperature to the crystallization temperature leads to an almost twofold increase in the degree of crystallinity. Lower molecular weight polyether ether ketone is characterized by a higher rate of crystallization and the formation of a more homogeneous crystalline structure.