In this study, we investigate the effect of terminal benzene derivatives in triphenylamine-based oxime esters on their photoreactivity. Five novel oxime esters ( Miko series) that containing different benzene derivatives as terminal groups, were synthesized. The electronic properties of the substituents on the benzene ring range from electron-donating to electron-withdrawing. Specifically, a methoxy benzene for Miko-MOB, tert-butyl benezene for Miko-t-Bu, chloro benzene for Miko-CB, trifluoromethyl benzene for Miko-TFM, and nitro benzene for Miko-NB. Additionally, a compound with benzene only as the terminal substituent (TP-1) was selected for comparision. All the new compounds exhibited higher molar extinction coefficients than TP-1. Additionally, the steady-state photolysis and electron spin resonance (ESR) properties would decrease from the electron-donating substitutes to electron-withdrawing substitutes. Finally, these oxime esters are utilized in Type I photoinitiating systems for the free radical polymerization of trimethylolpropane triacrylate (TMPTA) under UV or LED@405 nm light irradiation conditions. Among all formulations, Miko-MOB demonstrated the highest double bond conversion efficiency under both UV and LED@405 nm light irradiation. Thus, terminal benzene derivatives in oxime esters play an important role in tuning the optical and photochemical reaction performance, offering significant value for the design strategy of such photoinitiators.