We employed commercially available chip-calorimeter Flash DSC1 to investigate the low-temperature crystallization behaviors of random copolymer P(VDF-TrFE-CFE) (poly(vinylidenefluoride-trifluoroethylene-chlorofluoroethylene)), and compared them to the parallel results of P(VDF-TrFE). The resulted ferroelectric crystalline phases were identified by WAXD and FTIR. We found that, although our P(VDF-TrFE-CFE) contains higher content of VDF sequences than our P(VDF-TrFE), it performs crystallization of the ferroelectric phase at low temperatures much slower, and even exhibits cold crystallization upon heating back from fast cooling. We attributed the slowness to the effect of chemical confinement of large CFE comonomers. Our results facilitate better understanding of structural optimization for the electroactive applications of PVDF-based random copolymers. Display omitted •We first-time observed cold crystallization in fast-cooled P(VDF-TrFE-CFE).•Ferroelectric crystalline phase of VDF-TrFE sequences is generated at low temperatures.•Room-temperature transition of ferroelectric domains is vital for electrocaloric refrigerators.