Shape memory polymers are smart materials having the ability to change their shape under external stimulus. One of the most widely used shape memory polymers is cross-linked polyethylene (PE). The cross-linked polyethylene can be triggered by temperature to transfer from its permanent shape to programmed shape. Polyhedral oligomeric silsesquioxanes (POSSs) are the new generation of hybrid nanoparticles that positively affect the thermal stability, thermo-mechanical strength, flow properties and crystallization rates of the polymers. POSSs can also be used as crosslinking agents. Besides, coagents are used in order to improve the crosslinking efficiency by reducing undesirable side reactions such as chain breakage or disproportionation. They form bridges between polymer chains to be cross-linked. The aim of this study is to investigate the synergistic effects between POSS and coagent on the physical and shape memory properties of cross-linked linear low-density polyethylene (LLDPE). Octavinyl POSS (OvPOSS) nanoparticles and poly(ethylene glycol) dimethacrylate (PEGDMA) were used as coagents in this study. The peroxide used in crosslinking was di tert-butyl cumyl peroxide (PRX). Its content was kept constant as 1 phr. LLDPE/OvPOSS/PRX and LLDPE/OvPOSS/PEGDMA/PRX composites were prepared in an Xplore model micro-compounder at a screw speed of 50 rpm and 135°C barrel temperature. The crosslinking was carried out using a hot-press operated at 175°C. The samples were characterized by performing tensile tests, differential scanning calorimetry (DSC), scanning electron microscopy (SEM), rheology and shape memory tests. Rheological analysis showed that the degree of crosslinking, storage modulus and complex viscosity increased in the presence of OvPOSS and PEGDMA. A synergistic effect was observed between OvPOSS and PEGDMA coagents.