Triangulenes have attracted enormous interest due to the intriguing properties. However, the limited synthetic approach and intrinsic instability make the investigation of their properties inaccessible. The synthesis of heteroatom-doped triangulenes becomes an alternative strategy of studying triangulenes. Herein, we report the synthesis of three triangulenes, which are edge-modified by three oxygen-boron-oxygen (OBO) units. The structure of OBO-doped triangulene is confirmed by the single-crystal X-ray diffraction analysis, revealing an off-plane core with three edge-modified OBO units. These OBO-doped triangulenes exhibit high stability towards air and moisture. Both theoretical calculations and photophysical investigation of OBO-doped triangulenes indicate that this kind of molecules display anti-Kasha fluorescence and phosphorescence emissions. The binding behaviors of (OBO)3-triangulenes toward pyridine were also studied.