Green polyethylene is a new and attracting polymer from biobased resources (sugarcane) and identical properties to petroleum-based polyethylene. Its potential in the packaging industry is really promising. In this work, we report the use of different compatibilizer systems for green polyethylene (from sugarcane) and thermoplastic starch (30 wt% TPS) in order to increase ductile mechanical properties and biodegradable content. Typical petroleum-based graft copolymer of polyethylene with maleic anhydride (PE-g-MA) is used as reference compatibilizer, and new compatibilizer systems are developed using sepiolite. The obtained results show that sepiolite-based compatibilizers provide good compatibilization properties as observed by a remarkable increase in elongation at break and a noticeable size reduction of the TPS domains dispersed in the green polyethylene matrix as observed by scanning electron microscopy (SEM).