Nitriles, particularly acrylonitrile and acetonitrile, are versatile chemicals that are used in various fields, such as polymer synthesis and pharmaceutical production. For a long time, acrylonitrile has been produced via propylene ammoxidation with acetonitrile as a byproduct. The depletion of crude reservoirs and the production of unconventional hydrocarbon resources (e.g., shale gas) renders light alkanes (including propane, ethane, and methane) to be potential feedstocks in the syntheses of acrylonitrile and acetonitrile. In this review, the processes of transforming light hydrocarbons to nitriles are surveyed, the developments in nitrile synthesis from alkanes are discussed, and the existing challenges and plausible solutions are addressed.