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The study about the effect of the stacking mode on the photo/electrical performance of crystalline organic/inorganic hybrids will be beneficial for the design of new photo/electrically active materials. In this work, D–π–A stilbazolium-type chromophores bearing novel ortho-N-alkyl substituents were synthesized and incorporated with iodoargentates to generate three crystalline stilbazolium/iodoargentate hybrids, i.e., [(CMAMP)(Ag2I3)]n (1), [(HMAMP)(Ag2I3)]n (2), and [(HMAHP)2(Ag5I7)]n (3). When the substitutes on the amine group range from –C2H5CN (for CMAMP+) to –C2H5OH (for HMAMP+), the same (Ag2I3)nn− anions will be produced, and the π⋯π stacking interactions among stilbazoliums will be observed from absence to presence (weak head-to-head H-aggregation). Furthermore, when the substituent on the ortho-N of pyridine was also set as –C2H5OH (for HMAHP+), more electron-rich (Ag5I7)n2n− anion can be generated, and strong head-to-tail H-aggregation among HMAHP+ cations will happen. The enhanced aggregation strengthening in 3 can lead to its larger blue-shift photoluminescence, higher photocurrent, and better resistive switching performance (much higher ON/OFF ratio of 4.51 × 102). Their binary resistive switching mechanism can be explained as the SCLC model, and the better photo/electrical performances of 3 stem from its stronger head-to-tail H-aggregations, more negatively charged (Ag5I7)n2n− anion, and stronger (Ag5I7)n2n−–HMAHP+ interaction. The highly delocalized π antibonding orbitals between the empty p-orbitals of ethylene in its LUMO of (HMAHP)22+ dimer of 3 also support this conclusion. The good structure–property correlation based on accurate structural information in these stilbazolium/iodoargentate hybrids will be beneficial for the design of next-generation memory devices. [ABSTRACT FROM AUTHOR]