Polyhydroxy estolides were successfully synthesised from oleic acid through a non-catalytic one-pot method. Gel permeation chromatography (GPC) analysis showed that the yield of the polyhydroxy estolides was about 72% and the number average molecular weight (Mn) of the product ranges between 1000 – 2200 Da. Other instrumental analyses such as nuclear magnetic resonance (NMR), Fourier transform infra- Red (FTIR) and Matrix-assisted laser desorption/ionization-time of flight (MALDI-TOF) as well as acid value analysis revealed that the prepared polyhydroxy estolides was oligomers of dihydroxystearic acid linked by ester groups and further confirmation of the oligomers structure was achieved by reduction and saponification reactions.