The isothermal (IT) and non-isothermal (NIT) crystallization kinetics, morphology, and structure of poly(ethylene chlorotrifluoroethylene) (ECTFE) were investigated via differential scanning calorimetry (DSC), polarized optical microscopy (POM), and wide-angle X-ray diffraction (XRD). The Avrami equation could well describe the overall IT crystallization process of ECTFE, and, furthermore, the overall crystallization rate decreased at higher crystallization temperatures (T_c). The equilibrium melting point for ECTFE was found to be 238.66 °C. The activation energies for IT and NIT crystallization were determined as −137.68 and −120.54 kJ/mol, respectively. The Jeziorny model fitted well with the initial stages of NIT melt crystallization, while deviations from linearity in the later stages of the process were due to the collisions of spherulites. Spherulites of ECTFE organized in a hexagonal crystal system were found. The relative crystalline degree of ECTFE under NIT conditions was about 54.55%, and this decreased with the increase in cooling rate. Moreover, the Ozawa and Mo models were suitable for modeling the overall NIT crystallization process of ECTFE.