Flexible memory devices have continued to attract more attention due to the increasing requirement for miniaturization, flexibility, and portability for further electronic applications. However, all reported flexible memory devices have binary memory characteristics, which cannot meet the demand of ever-growing information explosion. Organic resistive switching random access memory (RRAM) has plenty of advantages such as simple structure, facile processing, low power consumption, high packaging density, as well as the ability to store multiple states per bit (multilevel). In this study, we report a small molecule-based flexible ternary memory device for the first time. The flexible device maintains its ternary memory behavior under different bending conditions and within 500 bending cycles. The length of the alkyl chains in the molecular backbone play a significant role in molecular stacking, thus guaranteeing satisfactory memory and mechanical properties.

It is discovered that the molecular packing and the orientation of crystallite arrangement in the film state are critical to the performance of the typical sandwich organic‐based memory devices (OMDs). Here, a solvent‐vapor annealing (SVA) strategy is firstly developed for amphipathic molecules to regulate the film morphology and intermolecular stacking, so as to obtain the satisfied performance. Through the screening of SVA solvents, an evidently upgraded nonvolatile memory behavior based on MeOH‐annealed film with superior reproducibility, a low switching voltage of −2.3 V and high ON/OFF ratio of 104 are observed. This work not only gives a fresh application of the amphipathic materials to OMDs, but really provides a general guiding significance for SVA solvent selection to achieve controllable crystallite orientation and effective OMDs performance.