Benzo[de]isoquinolino[1,8-gh]quinolinetetracarboxylic diimide (BQQDI) n-type organic semiconductors demonstrate unique multi-fold intermolecular hydrogen-bonding interactions that lead to excellent aggregated structures, charge transports, and electron mobility. However, the robust intermolecular anchoring of BQQDI presents challenges for further fine-tuning molecular assemblies and organic semiconductor properties. Herein, we report the design and synthesis of two BQQDI derivatives with sterically demanding phenyl- and cyclohexyl-substituted BQQDI (Ph–BQQDI and Cy6–BQQDI), where the two organic semiconductors show distinct molecular assemblies and degrees of intermolecular orbital overlaps. In addition, the difference in their packing motifs led to strikingly different band structures that give rise to contrasting charge-transport capabilities. As a result, Cy6–BQQDI shows excellent transistor performances in both single-crystalline and polycrystalline thin-film organic field-effect transistors.