This paper shows the effect of the nature of some alkaline activators in the microstructural development of thermal-alkali activated f/y ash systems. The alkaline compounds employed in this investigation were: NaOH, KOH, Na2C03, K2C03, sodium silicate and potassium silicate. Results confirm that the main reaction product of the activation process (throughout the studied systems) is the amorphous alkaline aluminosilicate gel with a three-dimensional structure already observed in earlier research. It has been proved that the type of anion and cation involved in the activation reaction of the ashes not only affects the microstructural development of the systems but the Si/Al ratio of that prezeolitic gel too. For example, in the presence of soluble silicate ions the content of Si in the final structure is notably increased (Si/Al =2.7-3.0), however carbonate ions play a different role since the formation of Sodium or Potassium carbonate/bicarbonate acidifies the system and consequently the reaction rate is considerably slowed. Finally it is evident that; when all experimental conditions are equal, sodium has a greater capacity than potassium to accelerate the setting and hardening reactions of fly ash and also to stimulate the growth of certain zeolitic crystals (reaction by-products). In general it can be affirmed that OH- ion acts as a reaction catalyst; and the alkaline metal (M+) acts as a structure-forming element.