In order to study the combined action of curing conditions and nano-silica (NS) on geopolymer concrete (GPC), the multi-based geopolymer concrete (FSSGC) was prepared with fly ash (FA), slag (SG) and steel fiber (SF), the experiments were carried out in three stages. Firstly, the mechanical properties of FSSGC was tested by monofactor analysis, with pre-curing temperature (20, 40, 60, 80, and 100 °C) and pre-curing time (6, 12, 18, 24, 30, and 36 h) as parameters. The compressive strength and splitting tensile strength initially increased and then decreased with the increase of parameters, and there was an optimal value for subsequent experimental research (80 °C and 18 h). Secondly, the effects of NS content (0, 0.5, 1.0, 1.5, and 2.0 wt%) on the mechanical properties of FSSGC under different curing conditions were analyzed. The results indicated that the mechanical properties of the FSSGC exhibited a trend of initially increasing and then decreasing with the increase of NS content, with the optimal mechanical performance observed under the combined action of high-temperature pre-curing conditions and the incorporation of NS (1.0 wt%). Thirdly, X-ray diffraction, scanning electron microscopy, image analysis, and microhardness tests had been conducted, and the results were consistent with the mechanical properties. The pre-curing temperature affected the rate of geopolymerization, while the pre-curing time influenced the degree of geopolymerization by maintaining this rate. The small particle size and high Young's modulus of the NS effectively filled pores and inhibited the propagation of microcracks. High-temperature pre-curing enhanced the nucleation effect and pozzolanic effect of NS, resulting in a combined action that formed a denser microstructure in the matrix and interfacial transition zone (ITZ).