The current shortage of donor organs in liver transplantation has led experienced transplant centers to use more "marginal" grafts. The development of a reliable technique of bile collection gives access to hepatic bile from donors and recipients for bile analysis to characterize the grafts. Proton nuclear magnetic resonance analysis has been applied to the study of bile for more than 30 years, showing encouraging results. This is the first study where proton nuclear magnetic resonance analysis has been applied to hepatic bile from selected liver grafts to evaluate its potential role in graft assessment. Hepatic bile was collected from eight liver donors (four with normal and four with steatotic grafts) during organ retrieval and four transplant recipients (two with good early graft function and two with primary dysfunction) immediately after graft reperfusion. A Varian Unity+ NMR spectrometer, operating at 11.7 Tesla (500 MHz for 1H), was used to obtain the proton nuclear magnetic resonance spectra. The results showed that the hepatic bile from steatotic grafts collected before transplantation had more intense phosphatidylcholine head group resonance than bile from normal grafts. It also showed slower clearance of University of Wisconsin solution in grafts with subsequent primary graft dysfunction, suggesting a slower recovery of bile secretion. These preliminary findings suggest that proton nuclear magnetic resonance analysis might help to differentiate the characteristics of bile acids and biliary lipids from normal and steatotic grafts. The monitoring of the resonance signal of University of Wisconsin solution washout, bile acid, and biliary lipid secretion may help to predict the development of primary graft dysfunction and avoid the need for retransplantation.