A novel metal-organic framework based on naphthalenediimide derivatives was synthesized, featuring ONDI2- ligands arranged in a slipped stacking pattern that forms H-aggregates with limited π-π interactions between two pairs of adjacent naphthyl carbon atoms. The compound demonstrates typical semiconductive behavior, with a conductivity of 3.1 × 10-7 S cm-1 at 30 °C. Density functional theory calculations suggest that the two pairs of naphthyl carbon atoms serve as the fundamental units for fabricating efficient charge transport paths, significantly contributing to the observed conductivity.