The influence of the alkaline activator (NaOH, waterglass, or Na2CO3) on the structure of the hydrated calcium silicate formed in alkali-activated slag (AAS) cement pastes has been investigated by FTIR, Si-29 and Al-27 magic-angle scattering nuclear magnetic resonance, and TEM/EDX techniques. In all cases, the main product formed after 7 d of activation, with activators giving an Na2O concentration of 4%, is a semicrystalline calcium silicate hydrate with a dreierkette-type anion. In these structures, linear finite chains of silicate tetrahedra (Q(2) units) are linked to central Ca-O layers, and tetrahedral aluminum occupies bridging positions in the chains. The main chain length and the amount of aluminum incorporated in the tetrahedral chains depend on the activator used. The detection of Q(3) silicon entities in alkaline-activated slags is discussed in relation to the possible formation of cross-linked structures that may be responsible for increased flexural and compressive strengths in AAS mortars.