Provided herein are dielectric fluids comprising at least one estolide compound of formula: in which n is an integer equal to or greater than 0; m is an integer equal to or greater than 1; R1, independently for each occurrence, 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. Also provided herein are uses of dielectric fluids and electrical devices such as transformers that comprise a dielectric fluid comprising at least one estolide compound.