The present article reports the synthesis of soluble, propyl‐substituted aromatic ring telechelic polycondensation blocks having molecular weights ranging from 1800 to 6500 g mol−1 and polymolecularities of 1.3 to 1.7. Chain‐growth polycondensation is performed, and the initiator is selected through reactivity studies, using 19F nuclear magnetic resonance (NMR) measurements. Gel permeation chromatography, NMR spectroscopy, and matrix‐assisted laser desorption/ionization time of flight mass spectrometry show that blocks are terminated by a methoxy group at one end and a fluorine atom at the other. Polymers are crystalline as synthesized, as shown by X‐ray diffraction and differential scanning calorimetry, do not recrystallize once melted, and undergo solvent‐induced crystallization. Crystalline peak positions and relative intensities are different from those observed for other poly(ether ketones). The difference in crystal form is proposed to stem from packing disruption related to the presence of propyl substituents. Thermogravimetry shows a good thermal resistance up to 450 °C.