Abstract We have previously reported a chiral photovoltaic (CPV) effect in a ferroelectric chiral smectic C (SmC*) phase of π-conjugated liquid crystals. This CPV effect is caused by the internal electric field originated from spontaneous polarization. The symmetry break caused by molecular chirality attributes the unconventional CPV effect, which is different from the bulk photovoltaic (BPV) effect in ferroelectric ceramics. In this study, enhancement of the CPV effect was achieved by the surface stabilization of the polarized state using 0.6-μm-thick liquid crystal cell and immobilization of polarization in an ordered chiral smectic phase by cooling down from the SmC* phase in the presence of an external electric field. The chiral fluorophenylterthiophene derivative (S)-1 exhibited a chiral smectic G (SmG*) phase below 125 °C and a SmC* phase between 125 °C and 140 °C. The value of spontaneous polarization was 68 nC cm−2 in the SmC* phase of (S)-1. The hole mobilities of (S)-1 were 2.7 × 10−4 cm2 V−1 s−1 in the SmC* phase and 2.3 × 10−3 cm2 V−1 s−1 in the SmG* phase. SmC*-SmG* phase transition in the presence of an external bias promoted the formation of polarized SmG* states. The photocurrent in the SmG* phase increased to 1.7 μA cm−2 in 0.6-μm-thick cells under 6 mW cm−2 UV light illumination, which was two times larger than that in the SmC* phase using 2-μm-thick cells. Photocurrent decay was completely suppressed in the SmG* phase using 0.6-μm-thick cell.