The proper control of the rheological performance of silicate-based alkali-activated slag (AAS) mixtures is problematic, as the conventional superplasticizers become less effective in alkaline media. Nevertheless, several methods have been proposed to improve the workability of silicate-activated AAS, such as by extending the mixing time, and replacing sodium silicate with sodium carbonate activators. However, the underlying fluidizing mechanism is not yet well understood in the literature, which is crucial knowledge to achieve proper rheology control of silicate-activated AAS. In this study, the effects of mixing conditions and activator anionic species on the rheology of silicate-activated AAS concrete have been assessed. The reaction products, particle size and interparticle interactions, as well as the reaction kinetics in AAS, have been further investigated to understand the distinct fluidizing mechanisms. By using a longer mixing time, it was found that the solid particles formed at early ages are broken down into smaller particles, accompanied by a slight increase in the amount of reaction products to improve the fluidity. With the sodium carbonate substitution, the calcium ions dissolved from slag particles are entrapped into calcium carbonate precipitates to slow down the accumulation of C-(A)-S-H phases, leading to a better dynamic flow. However, the interparticle interactions are intensified due to the formation of larger particles and the declined dispersing effect induced by silicate activators.