The recycling and reuse of waste concrete are crucial for reducing environmental pollution, minimizing resource waste, and lowering carbon emissions. However, current efforts to improve the performance of recycled cement (RC) using the synergistic effects of alkali activation and thermal activation have been suboptimal. Therefore, this study explores the influence of nano-silica (NS) incorporation on the mechanical properties and hydration mechanism of alkali-activated and thermally activated RC. The research focuses on cement mortar with a thermal activation temperature of 750°C, an RC replacement rate of 30%, and an alkali content of 6%. Various analytical techniques, including thermogravimetric analysis (TG-DTG), X-ray diffraction (XRD), and scanning electron microscopy (SEM), were used to evaluate the impact of different NS dosages (1%, 2%, 3%, and 5%) on the mechanical properties and hydration characteristics of nano-modified alkali-activated and thermally activated RC mortar. The study reveals the mechanism by which NS enhances the microstructure of alkali-activated and thermally activated RC. The experimental results show that as the NS content increases, the compressive and flexural strengths of RC initially increase and then decrease. The optimal strength was achieved with a 2% NS content, with a 31.5% increase in compressive strength compared to RC without NS. At this dosage, RC exhibited a higher hydration rate during the acceleration period of hydration. Additionally, the initial hydration heat release rate of RC increased with rising NS content. While NS incorporation did not alter the phase composition of RC, it activated the pozzolanic effect of RC, causing free active substances such as CaO and gypsum in the components to dissolve and react to form Aft at the start of the hydration reaction. The unsaturated bonds (≡Si-O- and ≡Si-) on the surface of NS absorbed Ca2⁺ and OH⁻ from the RC, promoting the hydration of C2S and C3S. However, excessive NS content (greater than 3%) led to a decline in RC strength and the formation of more cracks. This is primarily due to the excess NS particles not contributing to an increase in effective nucleation sites, causing agglomeration, an increase in large pores, and a reduction in transition and gel pores, which negatively affected the microstructure and thus reduced the mechanical properties of the RC. Our findings enhance the understanding of the role of nanomaterials in alkali-activated RC and provide valuable insights for further research into high-performance recycled cement materials.