An important strategy for realizing flexible complementary circuits with organic semiconductors is to achieve balanced ambipolar charge transport properties with reduced anisotropy. Here, we present a series of star-shaped diketopyrrolopyrrole (DPP)-based organic materials synthesized for improved intermolecular charge transport while retaining the ambipolar charge transport properties of their linear counterparts. Steady-state UV–visible spectroscopic studies confirm that the oligomers are highly aggregated in the thin film as evidenced from appearance of prominent vibronic features and red-shifted absorption bands. Ambipolar transport properties of these materials were verified in organic field-effect transistors (OFETs). The results show that the star-shaped DPP systems have the potential to outperform their linear counterparts in devices.