N-alkyl amines are an important class of molecules in the chemical industry and are extensively applied in the syntheses of dyes, pharmaceuticals, agrochemicals, surfactants, rubber ingredients, and functional materials. Given the importance of N-alkyl amines, the development of efficient synthetic methodologies to synthesize these amines is of broad interest. Among various methods, the catalytic alcohol amination has been viewed as effective and green method for synthesis of N-alkyl amines because alcohol is readily available, and water is generated as the sole by-product. This review describes developments and recent advances in the alcohol amination with different heterogeneous catalyst systems, including nickel, copper, palladium, platinum, cobalt, manganese, iron, gold, ruthenium, silver, and other catalyst systems. The frontiers and future of the topic are also given.