Mucoralean fungi are suitable microorganisms for the sustainable production of food, fodder, and fuels from inexpensive natural resources. Ethanol-producing Mucorales are particularly advantageous for second-generation ethanol production in comparison to the conventional ethanolic yeasts and bacteria. They are able to ferment a wide range of sugars to a range of valuable products, while they are typically resistance against the inhibitors available in different substrates, including untreated lignocellulosic hydrolysates. In addition to a high ethanol yield, the fungi produce several commercially valuable by-products, including chitosan, microbial oil (mainly polyunsaturated fatty acids), and protein. Moreover, the fungal extracts can replace the expensive nutrients required in fermentation. Besides, their morphologies can be altered from filamentous to yeast like and are adjustable based on the process requirement. The focus of this review is on applying Mucorales in producing ethanol and the biomass by-products thereof.