The in situ photopolymerization behavior of a ferroelectric Liquid-crystalline (FLC) monomer possessing a chiral moiety is discussed on the basis of molecular alignment in the liquid-crystalline phase. In an early stage of polymerization, the polymerizability of the FLC monomers was highest in the ferroelectric chiral smectic C (SmC*) phase in the absence of an external electric field. The polymerization behavior was found to depend mainly on the molecular alignment in the initial state of polymerization. In contrast, in the late stage of polymerization, the polymerization behavior of the FLC monomers was governed by their diffusion rather than their alignment. This may be due to the change in the phase structure during in situ polymerization. In addition, the alignment of the photopolymerized FLC was evaluated by optical polarizing microscopy. It was found that the application of an electric field to the FLC monomer resulted in the appearance of the immobilized SmC* phase, in which all mesogens of the resulting FLC polymer were aligned in one direction, leading to the formation of a monodomain of LC phase.