In the present study, two sugar-based perylenediimide derivatives (PDIs) substituted at the imide positions with carbohydrate groups were synthesized to investigate the impact of the stereoisomerism of the sugar on the aggregation morphology and optoelectrical properties. The results showed that right-handed and left-handed helical nanowire fibers were obtained in tetrahydrofuran (THF)/H2O solution for α-d-glucopyranoside- and β-d-glucopyranoside-substituted PDIs, respectively. Determination of the electrical current in hydrazine vapor revealed that both sugar-based chiral PDIs exhibited enhanced current changes compared to their achiral counterpart because of the larger π–π orbital overlap between their adjacent perylene cores. A larger π–π orbital overlap and a smaller π–π interplanar spacing increased the electrical current of the α-d-glucopyranoside-substituted PDI more markedly than that of the β-d-glucopyranoside-substituted PDI. The results of this study suggest that the stereoisomerism of chiral s...