A novel BN-fused coronene derivative 1,5,9-triaza-2,6,10-triphenylboracoronene (1) has been successfully synthesized in one step from 2,3,6,7,9,10-hexamethoxy-1,5,9-triamino-triphenylene. Compound 1 has been investigated using photophysical, electrochemical, and molecular simulation methods. Interestingly, three phenyl groups at B centers in compound 1 can be replaced by hydroxyl units stepwise through hydroxylation in wet organic solvents, leading to changes in the packing and physical properties.