The austempered ductile iron (ADI) grinding balls were austenitized at 900 °C for 2 h and then incomplete quenched in a sodium silicate solution for 100 s, after that austempered in an isothermal furnace at 230 °C for 1 h. Different from the two-step austempering process, this process can prepare a two-phase structure through the incomplete quenching stage and austempering stage, so we called it a dual-matrix structure (DMS) two-step austempering. This work aims to investigate the effect of different concentrations of sodium silicate (30 wt.%, 40 wt.%, 50 wt.% and 60 wt.%) as the incomplete quenching medium on the microstructure and properties of ADI. The microstructure, mechanical properties and wear resistance of ADI were analyzed using SEM with EDS, hardness testing (rockwell) apparatus and impact-toughness tester, as well as friction wear testing and impact wear testing. The result shows that the martensite and lower ausferrite phase in the DMS grinding balls gradually transform to lower ausferrite and upper ausferrite with increasing concentration of quenching liquid. As the sodium silicate concentration increased from 30 wt.% to 60 wt.%, the lower ausferrite volume fraction has initially increased and then decreased. DMS two-step austempering with a 40 wt.% sodium silicate produced the grinding balls with lower ausferrite and a small amount of tempered martensite that has the best overall mechanical properties and wear properties, which were suitable for application of large grinding machines. Besides, this work developed a new method to replace the salt bath austempering process, which was environmentally friendly.