Within the past four decades, matrix isolation spectroscopy has emerged as the method of choice for obtaining direct structural information on benzynes and related dehydroaromatics. In combination with quantum chemical computations, detailed insight into the structure and reactivity of di-, tri-, and tetradehydrobenzenes has been obtained. This Review focuses on rather recent developments in aryne chemistry with a special emphasis on the matrix isolation of tridehydrobenzenes and related systems.