In this case report we describe the blood metabolic profile (“metabolomics”) by nuclear magnetic resonance (NMR) spectroscopy and principle component analysis (PCA) from a patient who underwent two consecutive liver transplantations. The first graft from a living-related donor failed and was followed by a second successful transplant from a deceased donor. Using quantitative high-resolution 1H-NMR spectroscopy, 48 endogenous metabolites were analyzed in whole blood samples at baseline and different time points after each transplantation. From 48 analyzed metabolites, six metabolites were identified by PCA as metabolic markers consistent with a non-functional liver after first transplantation. Importantly, this distinctive metabolic profile was present as early as two hours after first transplant surgery when no other variable or conventional laboratory tests indicated poor graft function. This article reports the potential usefulness of quantitative 1H-NMR based metabolomics to diagnose early graft dysfunction in liver transplantation.