In this study, concretes and pastes were produced from a high MgO ground granulated blast furnace slag (MgO content 16.1 wt.%) by alkali activation with various amounts and combinations of sodium carbonate and sodium silicate. Sodium carbonate activators tended to reduce slump compared to sodium silicate at the same dose, and, in contrast to the literature for many blast furnace slags with more moderate MgO, to shorten the initial and final setting times in comparison with concretes activated by sodium silicate for dosages less than 10 wt.%. Higher heat curing temperatures and the use of larger dosages of alkali activators resulted in higher early age cube compressive strength values. The XRD analysis of 7 and 28 days old pastes activated with sodium carbonates revealed formation of gaylussite, calcite, nahcolite and C-(A)-S-H gel. Curing at 20˚C appeared to promote dissolution of gaylussite and calcite, while heat curing promoted their replacement with C-(A)-S-H, which also resulted in higher ultimate cube compressive strength values. Conversely, mixes activated with sodium silicate contained less crystalline phases and more disordered gel which strengthened the binder matrix.