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This invention discloses a triphenylamine-mediated photocatalytic isomerization method for olefins from E to Z, belonging to the field of organic synthesis technology. This invention uses triphenylamine and 4-nitrotriphenylamine, triphenylamine compounds, as photocatalysts to catalyze the E-Z isomerization of olefins. Their molecular structures have a propeller configuration, which can drive olefin configuration inversion through triplet energy transfer without the need for metal participation, achieving low-cost, highly stable, and mild E-Z isomerization of olefins. This invention is carried out at room temperature, without the need for high temperature and pressure, resulting in low energy consumption and environmental friendliness. It has a wide substrate applicability, exhibiting good catalytic activity for olefins with different substituents such as methyl, halogen, cyano, and hydroxyl groups, with product yields reaching up to 92%. The operation is simple, the reaction process is straightforward, and it is suitable for large-scale production applications.