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The effects of fine limestone powder on the early hydration of cementitious systems accelerated by means of alkali-free aluminum sulfate based products, commonly used for shotcrete applications, were investigated in the course of laboratory and real scale tests. In binary (CEM I + limestone) and ternary (CEM I + limestone + slag) systems the addition of fine limestone led to an enhancement of the hydration degree and strength development at early times (<24 h). The formation of ettringite, aluminate hydrates, and C–S–H is affected by the joint action of the setting accelerator and the fine limestone. Accelerator and limestone, in combination with the cement, can be optimized to enhance ettringite and silicate reaction, in some cases coupled with aluminate reaction inhibition, to produce mixes suitable for sprayed concrete applications. Such optimization can help to reduce the cement content in the mixes without compromising the early strength development of the shotcrete.