New symmetrically poly(ethylene glycol) (PEG)-decorated triglycerides of fatty acid are synthesized and proposed as drug-encapsulation systems. A method of effective grafting of PEG on secondary hydroxy groups located on long alkyl chains by the use of a short spacer represented by succinic acid is elaborated. Synthesis of new derivatives of triacylglycerols of fatty acids (TAG) based on the triolein standard and commercial olive oil, with PEG chains of different lengths (1000, 550, and 220 Da) is performed. MTT assay on the murine macrophage cell line RAW-262.7 shows the absence of cytotoxic effects caused by the obtained products. Encapsulation tests using itraconazole (ITZ) as a hydrophobic drug model are carried out. The influence of the PEG chain length, as well as of the presence of ITZ on the size of micelles, are studied by the dynamic light scattering (DLS) method. The reduced cytotoxicity observed on Candida albicans cells of ITZ formulated with the PEG-decorated TAG versus the free drug indicates that the systems may be promising to increase the duration of drug release and to reduce toxic side effects.