To further elucidate the influence of the polymeric units on PDI packing distortion, molecular dynamics (MD) simulations were applied to visualize the geometry of PDI-oligomers and their aggregates. First, we looked into isolated oligomers with 40 repeating units (PDI-tetraStx and PDI-tetraMMAx, x = 40), respectively, in DMF/H2O (5/95, v/v) (Figure , A and S8). As shown in Figure , the PDI core of PDI-tetraSt40 is well encapsulated in the polymeric styrene units. Interestingly, this was not observed in the case of PDI-tetraMMA40. Instead, one side of the PDI core is freely exposed to the environment with no shielding from the MMA units. This significant difference was also observed for PDI-tetraSt28 and PDI-tetraMMA28 (Figure ). The oligomer conformation was further systematically investigated for PDI-tetraStx, PDI-tetraMMAx, PDI-diStx and PDI-diMMAx with repeating units varying from 4 to 40, respectively, and the average percentage of encapsulated PDI core for each system was calculated. As shown in Figure , PDI-tetraStx showed increasingly high percentage as compared to other oligomers with increasing the chain length, which is pronounced when the DP is higher than 20. This result is in line with the PL emission intensity of the PDI polymers in aggregate state, indicating the joint impact from the electron-donating styrenic units and the star-shape architecture.