Substituents modification of BN-heterocycles on the boron atom has proven important to the photoreactivity and optoelectronic properties of BN-heterocycles. We developed a sequential and diverse synthetic strategy toward BN-heterocycles, in which the boron building block can be introduced with fully pre-functionalized substituents (Route A) or the substituents can be partially (Route B) or fully (Route C) modified after borylation. These three routes are complementary to provide more diverse BN-heterocycles, which will find broad applications in manipulating/controlling molecular transformations and the development of new photoresponsive materials.