Cyclopenta-fused B2N2-pyrene (B2N2CP) and diazaborepin (NBNM) have been accomplished from a same bi-indoles pre-cursor in three steps. Borylative cyclization of bi-indoles precursor with 2.0 equiva-lents BCl3 afforded NBNM as the major product, whereas increasing the BCl3 to 3.0 equivalents deliv-ered B2N2CP as the major product. Both B2N2CP and NBNM are highly emissive in solution. B2N2CP emit in deep blue region, while NBNM emit in the region of blue to green. Moreover, we found that flu-oride anion addition to the solution of B2N2CP and NBNM led to great change of their absorption and emission spectra.