A series of bio-based hybrid thermosets composed of maleinated acrylated epoxidized palm oil (MAEPO) and vinyl ester resin (VE) were produced using free radical-induced crosslinking. The amount of petroleum-based resin which was replaced by bio-resin (MAEPO) was varied from 5 to 20 wt%. The structure of the polymer systems was investigated by scanning electron microscopy and dynamic mechanical analysis. The mechanical properties of the VE/MAEPO resins were studied using tensile, flexural and impact tests. The result obtained from structural analysis revealed that for the polymer hybrids with up to 20 wt% bio-resin content, there is good compatibility between MAEPO and VE as no phase separation was observed for these systems. The prepared eco-friendly bio-based thermosetting resins exhibit remarkable improvement in toughness parameters, such as ductility and impact strength, thereby showing potential for use in composites and nanocomposites applications.