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Isoprenoid and branched glycerol dialkanol diethers (iso GDDs and br GDDs) have recently been detected in various environments, including sediment, soil and peat deposits. Their structures strongly resemble those of glycerol dialkyl glycerol tetraethers (GDGTs). Nevertheless, the origin of GDDs and their link to GDGTs remain unclear. Here we examined the concentration and distribution of iso GDDs and br GDDs, together with those of iso GDGTs and br GDGTs along a 4 m peat core from Tanzania. Whereas br GDDs have only been detected to date in their core lipid (CL) form, we report here, for the first time, br GDDs in both CL and intact polar lipid (IPL) forms, suggesting a biosynthetic origin for br GDDs. Concentrations of br GDGTs and br GDDs on one hand and of iso GDGTs and iso GDDs on the other hand, were observed to significantly co-vary ( R 2 0.49–0.58; p < 0.05), both for the CL and IPL fractions. Moreover, the fractional abundance of each GDD correlated significantly with that of its GDGT analogue ( R 2 0.33–0.97; p < 0.05). Taken together, the data show that GDDs and GDGTs are closely related and likely take part in common metabolic pathways, although the hypothesis of GDDs being degradation products of GDGTs cannot be excluded. [ABSTRACT FROM AUTHOR]