To investigate the effect of ferroelectric substrate with different polarization direction on the optoelectric properties of SnSe, SnSe thin-films were synthesized using pulsed laser deposition (PLD) in LiNO₃ substrate. SnSe thin-film with different thickness was prepared by tuning the deposition time. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) results show that high orientation single-phase SnSe thin-film was synthesized. Transmission electron microscope (TEM) image of the cross-section shows the high crystalline quality of the as-synthesized SnSe thin-film. In the darkness condition, for the polarization direction pointing to the thin-film, electrons would be introduced into SnSe thin-film, decreasing the conductivity of p-type SnSe. When the polarization direction points away from the thin-film, holes will be introduced into SnSe and thus enhance the conductivity of SnSe. Furthermore, the irradiation of 632 and 405 nm laser was used to test the effect of the coupling fields on the substrates with different polarization direction on the photoelectric effect. Both SnSe films on different polarization directions of LiNbO₃ show enhanced photoconductive effect because the 632 nm laser can only induce the photoelectric effect in SnSe thin-film. However, the 405 nm laser induces a completely different phenomenon. A typical band model was used to explain the regulation mechanism of SnSe photoconductive properties on ferroelectric polarization substrate with different polarization orientations.