The addition of a range of micro- and nano-particles to high-performance concrete has been the focus of recent research. At present, studies are mainly aimed at designing customised mortars, providing them with specific properties for each application. Improving the durability of mortars is one of the main objectives in such research, as a result of increasing environmental concern. The research presented herein analyses the synergistic effect of nanosilica and metakaolin as additives on the service life of cement-based mortars subject to aggressive environments (i.e., chloride exposure) at early ages. The effects of the additives on the durability properties of submerged samples after two and three days of curing were analysed. Tests were conducted on several different properties: resistivity, porosity, mechanical properties, chloride diffusion, and service life. It is observed that metakaolin and nanosilica exhibit a synergistic effect as additives, which is related to porosity refinement and chloride ion binding capacity, which contributes to enhanced resistance against chloride penetration from very early ages.