Photorefractive (PR) performances of methyl-substituted poly(triarylamine) (PTAA)-based PR device were demonstrated using chemically modified electrodes (CMEs) of self-assembled monolayer (SAM) coated indium-tin-oxide (ITO) electrodes. The SAM-ITO electrodes successfully suppressed dark current which blocks the formation of space-charge field and also causes the dielectric breakdown. The PR device consisted of composite of PTAA, 4-azacycloheptylbenzylidenemalononitrile (7-DCST), N-ethylcarbazole (ECz), and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) sandwiched between the SAM-ITO electrodes. The PR devices showed the PR performances: optical gain Γ, refractive index Δn, diffraction efficiency η, response time τ, sensitivity S, phase shift Φ, trap-limited field Eq, number density of traps NT, and space-charge field ESC. The remarkable response time of 11.3ms was achieved at the low electric field of 20Vμm−1, which was comparable to the response time of high-definition television (HDTV) quality of 16ms. Our approach will widen the usage of higher mobility materials to photorefractive field and give us more favorable materials to achieve the best performance of photorefractivity in the future.