Organic-inorganic hybrid materials with a high thermal stability and a low dielectric constant show great potential in the microelectronics industry. In this work, polyhedral oligomeric silsesquioxane-benzocyclobutenes (POSS-BCBs) were synthesized by a hydrosilylation reaction of octavinyloctasilasesquioxane (OVPOSS) and 4-(1,1-dimethyl-1-hydro)-silyl-benzocyclobutene with H 2 PtCl 6 as a catalyst. The ring-opening reaction of BCB on POSS-BCBs resulted in POSS-BCB resins with a highly cross-linked network structure. This resin exhibited good thermal stability (T 5% is 495°C in N 2 ), low dielectric constants (<2.1 at 20 MHz) and low water absorption.