In this research, we focus on the polymer-stabilized V-mode FLC (PSV-FLC) in which a doped monomer is photocured in the SmA phase. PSV-FLC may show monostable and V-shaped electrooptical characteristics with a grayscale capability. In this paper, we investigate the dependence of the monostable capability on the fabricating conditions such as monomer materials, polymer concentration, and UV energy. Furthermore, in order to increase the contrast ratio, we introduce a photo-alignment technique. As a result, it is found that the monostable capability of PSV-FLC strongly depends on their conditions. Furthermore, the more uniform molecular alignment without rubbing scratch pattern was obtained by using the photo-alignment film.