Polyhedral oligomeric silsesquioxane (POSS) is a unique molecule that is composed of an inorganic silica core with eight organic functional arms, which can be used as a nucleus for covalent bonding to create star-shaped block copolymers with improved mechanical and biological properties. In this work, highly porous star-shaped POSS-polycaprolactone-polyurethane (POSS-PCL-PU) films were synthesized as scaffold biomaterials for tissue engineering. These films have an interesting morphology consisting of rough spherulites with filamentous structures spreading out from their centers; the unique nanotopography was shown to be suitable for cell growth. In vitro degradation was monitored for 52 weeks in terms of the weight loss and morphology changes of the films. The degradation profile exhibited a slow initial weight loss of o1% during the first 24 weeks, followed by a rapid weight loss of~18% in the following 28 weeks. The films demonstrated excellent biocompatibility and cell-substrate affinity, with a high cell viability of 495% and rapid cell proliferation. The high porosity, unique surface nanotopography and excellent biocompatibility of the star-shaped POSS-PCL-PU film make it a great candidate as a tissue engineering scaffold biomaterial.