The aim of this study was to estimate parameters determining liver triglyceride composition (TC) using 1H MRS and to assess how TC estimability is affected by proton density fat fraction (PDFF) in adults with nonalcoholic fatty liver disease (NAFLD). In this prospective single‐site study, 199 adults with known or suspected NAFLD in whom other causes of liver disease were excluded underwent two 1H MRS STimulated Echo Acquisition Method (STEAM) sequences at 3 T. A respiratory‐gated water‐suppressed free breathing sequence (TE 10 ms, 16 signal averages) was used to assess TC in terms of the number of double bonds (ndb) and methylene‐interrupted double bonds (nmidb), and a single breath‐hold‐long TR, multi‐TE sequence (TR 3500 ms), which acquired five single average spectra over TE 10‐30 ms, was used to estimate liver PDFF. Ndb and nmidb estimability was qualitatively assessed for each case and summarized descriptively. The consistency of ndb and nmidb estimation was examined using ROC analysis. The relationship between ndb and nmidb values and PDFF was presented graphically. Quality‐of‐fit of ndb and nmidb versus PDFF was evaluated by Pearson‐r correlation. A significance level of 0.05 was used. In 263 1H MRS examinations performed on 199 adult participants, ndb and nmidb were successfully estimated in 7/53 (13.2%) examinations with PDFF < 4%, 13/30 (43.3%) examinations with PDFF between 4% and 7%, 33/41 (80.5%) examinations with PDFF between 7% and 10%, and 124/139 (89.2%) examinations with PDFF > 10% (maximum PDFF 38.1%). Liver TC could be estimated consistently for PDFF > 6.7%. Both ndb and nmidb decreased with increasing PDFF (ndb = 2.83‐0.0160·PDFF, r = ‐0.449, P < 0.0001); nmidb = 0.75‐0.0088·PDFF, r = ‐0.350, P < 0.0001). In a cohort of adults with known or suspected NAFLD, liver TC becomes more saturated as PDFF increases.