In this work we have investigated the influence of nanoscale and microscale structure on the tribo-mechanical performance and failure mechanisms of two biocompatible dental polymer composites, with different reinforcing particulates, using advanced microscopy techniques. Nano- and micro structural analysis reveals the shape, size and distribution of the particles in the composites. In the microparticle filled polymer composite (microcomposite), the particles are of irregular shape with sharp edges with non-uniform distribution in the matrix. However, in the nanoparticle filled composites (nanocomposite), filler particles are spherical in shape with uniform distribution in the matrix. From nanoindentation measurements, hardness and reduced modulus of the microcomposite were found to be heterogeneous. However, the hardness and reduced modulus of the nanocomposite were found to be homogeneous. The nanocomposite shows better tribo-mechanical performance compared to that of the microcomposite. © 2008 IOP Publishing Ltd.