Modification of π-conjugated systems using a boron atom as the dopant has become a powerful approach to create new structures and new properties. Herein, we report a facile synthesis of replacing the carbon edges of [4]triangulene by three oxygen-boron-oxygen (OBO) units. The OBO-modified [4]triangulenes are structurally similar to [4]triangulene and isoelectronic to the trianion of [4]triangulene. The structure of OBO-modified [4]triangulene is confirmed by single-crystal X-ray diffraction analysis, revealing an off-plane core with three edge-modified OBO units. These OBO-modified [4]triangulenes exhibit excellent thermal stability. These compounds have phosphorescence with lifetime longer than 1 s at 77 K. Both theoretical calculations and photophysical investigation of OBO-modified [4]triangulenes indicate that this kind of molecules display a rare anti-Kasha fluorescence and phosphorescence emissions from multiple higher excited states.