Glass transition temperature ( T g ) always deteriorates while improving the strength of epoxy resins which inherently suffer from brittleness. Herein, novel linear polyhedral oligomeric silsesquioxane (POSS)-epoxy nano-modifiers are synthesized with variable contents of POSS. The thermomechanical properties and chemical structure study of the POSS-epoxy indicates significant differences of the rigid POSS content in the linear nano-modifiers. By taking advantage of the synergistic effect of nanofillers and linear polymers, the modifiers disperse at the molecular level when POSS-epoxy is utilized as a co-curing agent for epoxy resins, allowing the applied force to be transferred into the polymer matrix. A good balance of T g , stiffness, and fracture toughness can be obtained. At 5 wt% of the nano-modifier, the resultant epoxy resins showed 27% enhancement in the Young's modulus relative to the neat epoxy. In addition, the T g and strength of epoxy thermosets are improved due to the increased cross-linking density, rough surface and tortuous path that resulted in good dispersion of energy during crack propagation.