Substitution of the C═C functionality with the isosteric and isoelectronic B-N moiety has emerged as a powerful way to expand the family of polycyclic aromatic hydrocarbons. In this paper, two types of BN-dinaphthothiophene (BN-DNT) derivatives with different B and N substitution patterns were synthesized in short steps from commercially available materials. X-ray crystallographic analysis revealed that BN-DNT 1 and 2 had rigid and planar frameworks. Their photophysical properties and the aromaticity of the BN rings of the BN-DNTs were slightly dependent on the B and N substitution patterns. However, their response toward fluoride anions was greatly dependent on the B and N substitution patterns.