A controllable synthesis was developed to prepare mono-estolide esters from α-hydroxyl fatty acids in order to improve the uncontrollability of estolide formation from unsaturated fatty acids. 2-Ethylhexyl α-hydroxyl dodecanoate (EHHD) was prepared in the first step esterification of α-hydroxyl dodecanoic acid with 2-ethylhexanol, and the target product 2-ethylhexyl α-dodecanoyloxy dodecanoate (EHDD) was synthesized in the second step esterification of EHHD with dodecanoic acid. The products were identified by FTIR, 1H NMR and ESI-MS and the final product was verified as a estolide 2-ethylhexyl ester with 32 carbon atoms and a character of EN (estolide number) = 1. The melting point of EHDD is -45.34 ℃ measured by DSC method.