A truxene derivative (Tr3) with a C3 symmetric conjugated plane is synthesized; this derivative is a perfect match, in both size and structure, with its oxidized counterpart, the truxenone derivative (TrO3), a new electron acceptor that was recently reported. The complementary pair, Tr3 and TrO3, sets a good platform for the investigation of aromatic donor–acceptor interactions. Detailed 1H NMR experiments, photoluminescence spectroscopy, as well as differential scanning calorimetry are performed to investigate the interaction between Tr3 and TrO3, from solution to mesophase. One-dimensional microbelts readily formed from a 1:1 mixture of Tr3 and TrO3. Scanning electron microscopy, powder X-ray diffraction, as well as fluorescence microscopy are performed to elucidate their co-assembly structure in the solid state. Moreover, modulation of the co-assembly structure is easily realized by changing the concentration or mixing ratio. The present system opens the possibility of forming 1D heterostructures via electron donor–acceptor interaction, and its potential application as P–N junction and photowaveguide materials in optoelectronic devices.