The high hydration potential of CaO and MgO phases restricted the application of Mag-Dol refractory composites. In this study, the impact of nano-silica (SiO2) addition on the physical, mechanical, thermo-mechanical as well as microstructure of Mag-Dol refractory composites is investigated. Mag-Dol compositions were prepared by using calcined dolomite and magnesite particles (micron, 0–1, 1–3, 3–5, and 5–8mm), liquid resin, and 0, 0.5, 1, 1.5, 2, and 2.5wt% nano SiO2 as additives. Specimens were heated up to 1650°C for the 3h soaking period. Fired specimens were characterized by physical (apparent porosity, bulk density, and hydration resistance), mechanical (cold crushing strength), and thermo-mechanical (flexural strength at 1200°C) measurements. XRD and SEM/EDS analysis were done to study phases and microstructure analysis of the fired samples, respectively. Results showed that by adding up to 2.5wt% nano-SiO2, due to the formation of CaO·MgO·2SiO2 (Diopside), 2CaO·MgO·2SiO2 (Akermanite), and CaO·MgO·SiO2 (Monticellite) phases, physical and mechanical properties were enhanced. But the highest flexural strength value is achieved for 1wt% nano-SiO2 containing sample.