From the viewpoint of the improvement of organic optoelectronic devices, including organic electroluminescence devices, organic solar cells, and organic field effect transistors, development of novel pi-conjugated molecules with unique structures and properties should be of great importance. In the course of our study on functional pi-systems by taking advantage of characteristics of main group elements, we have synthesized dibenzoheteraborin-based hetero-pi-conjugated molecules. Rigid and planar pi-backbones of the dibenzoheteraborin derivatives have been shown to enhance synergetic interactions between the main group elements. In this paper, syntheses and properties of the dibenzoheteraborin derivatives involving various main group elements, such as nitrogen, oxygen, phosphorus, sulfur, and selenium, are described.