Mexico 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 ( 13 C 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 1144