Blood chemical parameters were analyzed by Fourier-transform infrared spectrometry (notably for determining the concentrations of glucose, lactate, urea, glycerol, triglycerides, and proteins) in 14 top-class marathon runners (133.7±4.1 min at marathon, 10.1% difference between extremes) who performed a 10-km run at their individual marathon velocity. Marathon performance level was correlated to glycemia increase during exercise (9% difference between extremes; r=0.93; p<0.005). The best marathon runners presented longer and/or less unsaturated blood fatty acids during exercise (17% difference between extremes; r=0.89; p<0.01), suggesting an improved fatty acid selectivity for muscular metabolism. The marathon performance level was also found correlated to a decrease of blood triglycerides during exercise (r=20.95; p<0.003) and to a proportional glycerol concentration increase (11% difference between extremes; r=0.94; p<0.005). The best marathon runners presented higher amino acid blood delivery (r=0.88; p<0.01), which was correlated to an apparent protein catabolism. These results show that the best runners have enhanced both carbohydrate, lipid, and amino acid metabolisms to improve energetic supply to skeletal muscle during exercise.