The photoresponsive wormlike micelles constructed by Gemini surfactants and cinnamate derivatives play a great role in the field of smart materials. However, how the structure of cinnamate derivatives affects the photoresponsive behavior of micelles is still a hotspot for scientists to research. Here, three kinds of aromatic salts with different ortho-substituted groups including trans-o-methoxy cinnamate (trans-OMCA), trans-o-hydroxy cinnamate (trans-OHCA), and trans-cinnamate (trans-CA) were introduced into Gemini surfactant 12-3-12.2Br(-) aqueous solutions to construct photoresponsive wormlike micelles through their noncovalent interactions. Their properties were researched using the rheological method, cryo-transmission electron microscopy, and H-1 NMR and two-dimensional nuclear Overhauser effect spectra. The results show that these cinnamate derivatives could well construct wormlike micelles with 12-3-12.2Br(-). Furthermore, subtle differences in the ortho substituents' structure have a significant effect on the photoresponsive behavior of formed wormlike micelles. Specifically, the zero viscosity (eta(0)) of 40 mM 12-3-12.2Br(-)/24 mM trans-OHCA mixed solution decreases from 26.72 to 2.6 Pa.s with the shortening of the length of wormlike micelles after UV irradiation. Correspondingly, the eta(0) for the same ratio of 12-3-12.2Br(-)/trans-OMCA decreases from 2.42 to 0.06 Pa.s and the wormlike micelles are transited into rodlike micelles and even spherical micelles after the same UV irradiation time. However, the variation of wormlike micelles in the 12-3-12.2Br(-)/trans-CA system induced by UV light is not obvious with eta(0) being maintained at around 2.89 Pa.s. This study will help us better understand the effects of chemical groups on macrophenomena and microinteraction for micellar systems. It provides a theoretical basis for the construction of photoresponsive micelles, thus widening their application in the field of soft materials.