Highly reactive intermediate “benzyne” have long been attracted chemists. Benzyne reactions are particularly useful because various aromatic compounds can be synthesize in a few steps under mild reaction conditions. However, there still remain several serious issues such as low regioselectivities of unsymmetrical benzynes and functional group installations onto benzyne precursors. Under such background, we have been working on developing new methods to control the regioselectivities and to prepare functionalized benzynes. In this lecture, our current work on benzyne chemistry including novel theoretical studies would be presented.