AbstractMexico is one of the largest agricultural producers in Latin America and generates a large amount of agricultural residue. The aim of this study was to establish the usefulness of four of the main Mexican crops (corn, wheat, sugarcane, and Agave) as feedstock for lignocellulosic bioethanol production. The lignocellulosic residue ratio (RR), defined as weight of residue (in tons) per ton of product, was measured by sampling crop fields in 11 geographic regions of Mexico. The chemical composition, assessed by Fourier‐transform infrared spectroscopy (FTIR) and carbon‐13 nuclear magnetic resonance (13C NMR), and structural composition (extractives, cellulose, hemicellulose, and lignin contents), heating value, and metal content of these lignocellulosic residues were measured. Biorefinery locations, and their theoretical bioethanol production, were suggested using the gravity center method and techno‐economic criteria. The highest RR (1.1 ton of straw per ton of grain) was obtained for wheat straw followed by corn (0.8 ton of stover per ton of grain), sugar cane (0.15 ton of bagasse per ton of cane), and Agave (0.2 ton of bagasse per ton of stem). The composition of these biomasses varied significantly depending on the parental material in extractive compounds, lignocellulosic matter, ashes, hemicellulose, lignin, O‐alkyl C, aromatic C, and carboxyl C. The cellulose crystallinity index and the heating value exhibited small variations among biomasses. Copper, Zn, Cd, and Ni content in the biomasses generally exceeded the European Norm (EN‐Plus FprEN 1496 1‐2 B) for solid biofuels. In total, these agricultural biomasses could be used as feedstock for 34 biorefineries in Mexico with a total bioethanol production potential of approximately 1246 million L year–1. © 2019 Society of Chemical Industry and John Wiley & Sons, Ltd