Nickel-based alloys exhibit excellent mechanical properties, oxidation resistance and corrosion resistance, and are therefore widely used in aerospace equipment. However, when the alloys represented by NiCrAlY are in service in harsh marine environments, the continuous oxide protective film on the surface is destroyed, leading to a serious reduction in engine life. Therefore, the development of new nickel-based alloy systems and the evolution of their surface structures are of great significance. Based on the phase diagram, new NiSiAlY system was designed for nickel-based alloys in harsh marine environments. Through multi-scale theoretical calculations and key experiments, the evolution of the surface structure of the alloys was revealed before and after oxidation or corrosion. The oxidation results indicated that the higher the Si content in the alloy, the thinner the outer layer of NiO and the inner layer of oxidation; the corrosion results showed that: The introduction of Si caused the formation of SiO2 on the corrosion alloy surface and reduced the potential difference between γ/γ' and Ni5Y. Therefore, through the addition of appropriate elements and composition optimization, the surface structure control of nickel-based alloys for harsh marine service can be regulated, thus further enhancing the oxidation resistance and corrosion resistance of the alloys.