This study investigates the effects of five different super-plasticizers (SPs): melamine sulfonate (M), naphthalene-based (N), lignosulfonate (L), polyether-type (P-I), and polyester-type polycarboxylate super-plasticizers (P-II), on fly ash through fluidity, viscoelasticity, inter-microstructure, and mechanism of action (adsorption and zeta) experiments. Additionally, the stability of SPs on AAs was investigated in the ATR-FTIR experiment. The results show that most SPs were effective admixtures under high Ms (2.25) of waterglass (WG) alkali activators (AAs), while P-I SPs performed better under low Ms (1.0) of WG AAs in FA-AAM fly ash pastes. Meanwhile, the higher adsorption and zeta values of samples with P-I SPs were useful for the increase of mesh size of inter-particles and consequently promoted the rheology of FA-AAMs fresh pastes. The more stable structure (ether bond) and the formation of small functional groups (carboxylic acid groups) of P-I SPs in the AAs environment may be the main reasons for this.