This paper reports the preparation of newly synthesized sugar-based epoxy monomers, suitable for replacing petrochemical-derived epoxy resins of high thermal stability. Several bi- tri- and tetrafunctional epoxy components were prepared from d-glucose, among them the glucopyranoside- and glucofuranoside-based trifunctional ones proved to be the most promising for high-tech applications. The applicability of the synthesized compounds as epoxy monomers was investigated by curing probes with a model aromatic amine-type hardener. The curing enthalpy of the bioepoxy resins were examined, and compared to theoretical values, as well as the glass transition temperature, which is a crucial parameter when determining the potential fields of application of the bioresins. Tg values up to 175°C were reached, while the thermal degradation of the cured resins start at around 300°C.