In this work, polyhedral oligomeric silsesquioxane‐graphene oxide (POSS‐GO) was prepared by 1,6‐Hexanediamine (HDM) as a bridge and characterized using Fourier transform infrared spectroscopy, thermogravimetric analysis, X‐ray diffraction, and transmission electron microscope. High thermal conductivity toughening composites were prepared by introducing POSS‐GO into epoxy resin (EP) with solution blending. The introduction of HDM‐POSS molecular chain can not only improve the dispersion of GO in epoxy, but also as “stent” prevent the accumulation of GO. Results show that when the weight loading of GO and POSS‐GO was 1.0 phr, the thermal conductivity of composites improved by 26.32 and 63.16% as compared with neat epoxy. Impact strength of POSS‐GO/EP is 29.29% higher than that of GO/EP at 0.8phr and bending strength tests also showed similar results. When compared with pristine GO, POSS‐GO possessed better thermal conductivity and toughening effect for epoxy, moreover, the mechanism is discussed in this paper. POLYM. COMPOS., 39:E1890–E1899, 2018. © 2018 Society of Plastics Engineers