A Brønsted-acid-promoted alkyne benzannulation approach was developed to synthesize the amino-substituted dibenze[ a, j]anthracence derivatives in excellent yields, which were directly converted to fully zigzag-edged polycyclic heteroaromatic hydrocarbons via a nitrogen-directed electrophilic borylation. As the dopant in a blue-green electroluminescent device, the resulted compound exhibited relatively high stability.