A facile method was proposed to control the morphology and enhance the ultimate mechanical properties of polyethylene/polystyrene (PE/PS) by incorporating Gemini‐surfactant‐ organically modified montmorillonite (OMMT). OMMT was synthesized and incorporated into the immiscible PE/PS to fabricate composites. The effect of OMMT modified with a surfactant of different carbon chain length on the morphology and the final properties of the immiscible PE/PS polymer composites were investigated. FTIR and X‐ray diffraction characterizations revealed OMMT was successfully synthesized. Scanning electron microscopy observation revealed the morphologies of the PE/PS (70/30, w/w)/OMMT composites gradually transformed from “sea‐island” into the co‐continuous structure with the increase of the OMMT loading. The elongation at break of the PE/PS compatibilized with 1.5 wt% of Gemini C10‐MMT can reach as high as 700%. When compared with the PE/PS without OMMT, the flexural strength and modulus of the PE/PS/OMMT composites also have a remarkable enhancement with OMMT content. The flexural modulus of the PE/PS/OMMT composites with 1.5 wt% Gemini C10‐MMT was increased by 22%. POLYM. COMPOS., 40:3254–3263, 2019. © 2018 Society of Plastics Engineers