A truxene derivative (Tr3) with a C-3,C- 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, T;r3 and TrO3. sets a good platform for the investigation of aromatic donor-acceptor interactions. Detailed H-1 NMR experiments, photoluminescence spectroscopy, as well as differential scanning calorimetry are performed to investigate the interaction between T;r3 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. Morever, 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.