The rule-of-mixture approach has become one of the widely spread ways to investigate the mechanical properties of nano-materials and nano-structures, and it is very important for the simulation results to exactly compute phase volume fractions. The nanocrystalline (NC) materials are treated as three-phase composites consisting of grain core phase, grain boundary (GB) phase and triple junction phase, and a two-dimensional three-phase mixture regular polygon model is established to investigate the scale effect of mechanical properties of NC materials due to the geometrical polyhedron characteristics of crystal grain. For different multi-sided geometrical shapes of grains, the corresponding regular polygon model is adopted to obtain more precise phase volume fractions and exactly predict the mechanical properties of NC materials.