Using a first-principles plane-wave pseudopotential method, the energetics and electronic structures of Ni/Ni3Al interface with Re and Ru additions have been calculated. The calculation of Griffith rupture work W demonstrated that either the substitution of Re atom for Ni atom in γ-Ni block or Ru atom for Al atom in γ＇-Ni3Al block are profitable to improve the rupture strength of the interface. The multiple addition of Re and Ru can further improve the strength of the interface when Re and Ru atoms occupy respectively at Ni and Al sites at （001） atomic layers adjacent to the coherent （002） interfacial atomic layer. Whereas, when Ru atom locates at Al site in γ＇-Ni3Al block and far away from the coherent （002） interfacial layer, the multiple addition will decrease the interface strength to a lower value than that with only Ru addition. The analysises of electron densities of states （DOS） and the distributions of valence electron densities revealed that the effect of Re and Ru is attributed to the stronger electronic interactions of Re-Ni and Ru-Ni within first nearest neighbor.