Olefins find widespread applications in the synthesis of polyolefins and fine chemicals. With an increasing demand for olefins, the technologies for alkane dehydrogenation have drawn much attention. Several types of heterogeneous catalysts have found applications in industry for the dehydrogenation of light alkanes, mainly ethane, propane, and butane. In the past three decades, a number of transition-metal complexes, particularly pincer-ligated iridium complexes, have been developed as the homogeneous catalysts for alkane dehydrogenations. The homogeneous catalyst systems operate under much milder conditions compared with the heterogeneous systems, and some systems exhibit good activity and high regioselectivity in dehydrogenation of alkanes longer than butane.