Novel biobased high functionality epoxy resins were synthesized by the epoxidation of sucrose ester resins of vegetable oil fatty acids (SEFA). A series of sucrose esters of fatty acids were epoxidized by peracetic acid generated in situ from hydrogen peroxide and acetic acid in the presence of an ion exchange resin catalyst to produce the epoxidized sucrose esters of fatty acids (ESEFA). The conversion of double bonds to epoxides was greater than 99%. The products were characterized by matrix-assisted laser desorption and ionization time-of-flight (MALDI-TOF) mass spectrometry, Fourier-transform infrared (FTIR) spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy. The physical properties were characterized using bulk viscosity, intrinsic viscosity, and density measurements. The thermal properties were characterized by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Since sucrose esters consist of a sucrose core fully substituted with eight vegetable oil fatty acids, both SEFAs and ESEFAs possess well-defined compact macromolecular structures. As novel biobased epoxy compounds, ESEFAs possess high epoxy functionality (8–15 per molecule), high density, and a compact molecular structure. Thus, ESEFAs are very promising in a number of uses from the formation of biobased thermosets by crosslinking of the epoxy groups, to further derivatization by reaction of the epoxy groups.