It is well documented that chemical additives (grinding aid "GA") during grinding can increase mill throughput, reduce water and energy consumption, narrow the particle size distribution of products, and improve material flowability. These advantages have been linked to their effects on the rheology, although there is a gap in understanding GA effectiveness mechanism on the flow properties. The present study aims to fill this gap using different GAs (Zalta™ GR20-587, Zalta™ VM1122, and sodium hydroxide) through batch grinding experiments of magnetite ore and addressing the mechanisms of their effects on the rheology by an FT4 Powder Rheometer as a unique system. Experimental results showed that GA improved grinding efficiency (energy consumption and product fineness), which were well-correlated with basic flow energy, specific energy, aerated basic flow energy, and aerated energy. Moreover, the rheometry measurement showed strong linear correlations between basic flow energy, specific energy, and the resulting work index when GAs was considered for grinding, which confirmed the effect of GA on ground particles' flowability. Zalta™ VM1122, a polysaccharide-based grinding aid, showed the best performance with 38.8% reduction of basic flow energy, 20.4% reduction of specific energy, 24.6% reduction of aerated basic flow energy, and 38.3% reduction of aerated energy. It also showed the strongest correlation between the grinding parameters and flow parameters (r > 0.93). The present investigation shows a strong indication that the predominant mechanism of GAs is based on the alteration of rheological properties and identify Zalta™ VM1122 as the best GA.