Nitriles are synthetic intermediates of great importance, so it is significant and appealing to develop novel approaches for the green synthesis of these compounds. Compared with other synthetic strategies, the ammoxidation of alcohols over heterogeneous catalysts emerges as a sustainable process for the preparation of nitriles owing to its atom and step economy, and the use of cheap and sustainable raw materials and recyclable catalysts. In this review, we summarized the latest progress in developing heterogeneous catalysts to achieve the transformation of alcohols into nitriles. Furthermore, this review not only introduces the preparation and functionalization strategies of heterogeneous catalysts, but also discusses the reaction mechanism and the roles of heterogeneous catalysts in these reactions.