•Alkali-activated fly ash with pozzolanic reaction reached 60 MPa at ambient condition.•Silica fume enhanced reaction participation of Ca2+ in alkaline environment.•Significant contribution to strength development was induced from pozzolanic reaction.•Physical filling effect by addition of silica fume was negligible in tested mix proportions. Despite considerable efforts focused on the utilization of industrial wastes, the application of low-calcium fly ash to the construction industry is limited to the partial substitution to ordinary Portland cement. High-temperature curing is a method via which fly ash can be completely utilized as an alkali-activated construction material; however, additional energy is required. In this study, the dual reaction of alkali activation and the pozzolanic reaction was proposed to manufacture ambient-condition-curable structural mortars. For this purpose, calcium hydroxide was used in fly ash activated by sodium hydroxide and sodium silicate solutions. A series of experiments, including compressive strength tests, X-ray diffraction, thermogravimetric analysis, heat of reaction, and mercury intrusion porosimetry, were conducted. The continuous pozzolanic reaction on the pre-formulated geopolymeric skeleton was found to significantly enhance the material properties. By the addition of silica fume and a 7:3 mixture of sodium hydroxide and sodium silicate solutions, the material strength increased to greater than 60 MPa at 56 days. The added silica fume as well as the reduced alkali content of the solution enhanced the reactions due to the active participation of the calcium ion supplied by the added hydrated lime in a high pH environment.