This research aimed to evaluate the performance of sprayed shotcrete mixtures prepared by silicate-based and alkali-free accelerators. A new innovative silicate accelerator was used at dosages of 4% and 6% and was compared to a standard silicate accelerator and an alkali-free accelerator at dosages of 6% by binder weight. Scaled-down shotcrete elements were cast to investigate the different shotcrete mixtures’ behaviour. The mechanical and microstructure properties of shotcrete mixtures at different curing ages were investigated. Results proved the competitive behaviour of the innovative silicate accelerator compared to other accelerators. Also, the new innovative silicate-based accelerator had less tendency to reduce mixtures’ compressive strength at a later age, up to 90 days.