It has been shown that a polymer network, formed in the SmA phase by UV photocure of photocurable liquid crystalline monoacrylates that are doped in a surface-stabilized ferroelectric liquid crystal (SSFLC), eliminates zig-zag defects in the SmC* phase, Since a chevron layer structure is transformed into a quasi-bookshelf layer structure by the polymer main chain. In this study, we have observed the electrooptical (EO) effect of this polymer-stabilized SSFLC (PS-SSFLC) with the aim of exploring the effect of the liquid crystalline polymer network on the alignment structure of FLC molecules. As experimental results, it was found that liquid crystalline side chains bond strongly with a main chain and attract FLC molecules in the rubbing direction. Furthermore, we propose and demonstrate a new PS-SSFLC fabricated also by UV photocure of doped monoacrylates particularly at a temperature where the LC medium is in the SmC* phase under the simultaneous application of a monopolar electric field. This device exhibits monostable EO characteristics with a high contrast ratio owing to being defect free, having grayscale capability without threshold, and a fast response speed.