Purpose To assess the proton T1 and T2 relaxation of in vivo hepatic water, choline and lipid resonances with possible J‐coupling behavior of lipids in healthy volunteers at 7 Tesla (T). Materials and Methods Relaxation measurements were conducted on corn oil phantoms and on the hepatic tissue of 11 healthy volunteers at 7 T using a surface coil and a STEAM sequence. T1's were determined by monoexponential fitting, and T2's by both monoexponential and enhanced‐exponential fitting (empirically designed to consider J‐coupling of lipid resonances). Results In vivo T1's at 7 T were estimated as follows: water (4.70 ppm), 1362 ± 83 ms; methyl‐ (0.90 ppm), 1026 ± 162 ms; methylene‐ (1.30 ppm), 514 ± 25 ms; α‐olefinic‐ (2.02 ppm), 488 ± 220 ms; α‐carboxyl‐ (2.24 ppm), 476 ± 89 ms; diacyl‐ (2.77 ppm), 479 ± 260 ms group of lipid chains; and choline compounds (3.22 ppm), 1084 ± 52 ms. The T2's calculated with enhanced fitting were as follows: water, 15 ± 2 ms; methyl‐, 34 ± 10 ms; methylene‐, 41 ± 8 ms; α‐olefinic‐, 44 ± 19 ms; α‐carboxyl‐, 39 ± 15 ms; diacyl‐, 44 ± 5 ms group of lipid chains; and choline compounds, 32 ± 9 ms. Conclusion An accurate knowledge of in vivo relaxation and J‐coupling behavior will significantly improve the quantification of an extended number of resolved liver metabolites at 7 T. J. Magn. Reson. Imaging 2014;40:1365–1374. © 2013 Wiley Periodicals, Inc.