Porous TiB2 ceramics with a three-dimensional interconnected skeleton were fabricated by high temperature pressureless sintering from fine TiB2 powders. The microstructure of the porous TiB2 ceramic was characterized by the enhanced neck growth between the initially touching particles. This neck growth was ascribed to the selective heating of TiB2 particles with different dimension. The porous structure prepared by the high-temperature sintering exhibited higher bending strength and fracture toughness in the present experiment. The improved mechanical properties of the sintered composites were attributable to the enhanced neck growth by surface diffusion.