Provided herein are poly-capped estolides, including those of the Formula IV in which n is an integer equal to or greater than 0; m is an integer equal to or greater than 2; R1 is selected from optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched; R2 is selected from hydrogen and optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched; and R3 and R4, independently for each occurrence, are selected from optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched. Hydroxy estolides are also described herein, which may be suitable end products, or serve as intermediates to provide poly-capped estolides. Also provided are compositions containing poly-capped estolides and methods of making both said poly-capped estolides and compositions thereof.