A diversity-oriented one-pot synthesis of a series of membrane-permeable BF2-rigidified benz[c,d]indole N-heteroarene BBN and BBC dyes has been achieved from the condensation of two commercial components (benz[c,d]indol-2-one and a set of N-heteroarene derivatives that can be selected from thousands of commercially available sources) and the subsequent in situ BF2 complexation reaction. These dyes enjoy a set of excellent photophysical properties including the large Stokes shift, high solution and solid-state fluorescence, and excellent photostabilities.