Discrete element method (DEM) is a useful tool for obtaining details of mixing processes at a particle scale. It has been shown to satisfactorily describe the flow structure developed in bladed mixers. Here, the advantage is taken of the microstructure gained from DEM to evaluate how best to quantify the microstructure created by mixing. A particle-scale mixing index (PSMI) is defined based on coordination numbers to represent the structure of a particle mixture. The mixture quality is then analyzed qualitatively and quantitatively in three different ways: a macroscopic mixing index based on the conventional approach, coordination number, and PSMI. Their effectiveness is examined based on DEM data generated for different particle loading arrangements and binary mixtures of particles with various volume fractions, size ratios, and density ratios. Unlike the two other methods, PSMI reveals in a straightforward manner whether a binary mixture of different particles is mixing or segregating over time, while being able to detect particle-scale structural changes accompanying the mixing or segregation processes in all the mixtures investigated. Moreover, PSMI is promising in that it is not influenced by the size and number of samples, which afflict conventional mixing indexes.