We developed an efficient strategy to construct a series of tetracoordinate boron-doped PAHs with various substituents on boron atoms at room temperature. Some of them were successfully converted to a fully fused four-coordinate borondoped NBN-PAHs via oxidative coupling. The substituents on boron atoms were found to have negligible impact on photophysical and electrochemical properties. All the rings with tetracoordinate boron atoms are antiaromatic. The fused NBN-PAHs display blue-shifted AIE behavior.