Attributed to the characteristics of narrow band gap structural units and full spectral response, iso‐indigo is often used as an electron acceptor in organic electronic materials. Organic molecules with large conjugated surfaces and strong intermolecular forces can form ordered stacked structures through self‐assembly. In this paper, the self‐assembly performances of IDCF3 and IDCN are regulated by changing the end groups. The effects of terminal groups on the resistive memory behaviours and reproducibility are investigated. The properties of IDCF3 and IDCN devices are characterized by UV‐VIS spectroscopy, cyclic voltammetry and DSC diffraction. The results show that when the end groups with different steric hindrance are introduced into the ends of the molecules with good backbone plane, the conjugated surfaces of the molecules will bend due to the different steric hindrance of the end groups in the form of cambium and layer‐ordered packing, which will affect the threshold voltage and device reproducibility.