There is provided with a silver ink composition which is formed by blending one or more kinds of silver β-ketocarboxylates selected from the group consisting of silver isobutyrylacetate, silver benzoylacetate, silver propionylacetate, silver acetoacetate, silver α-methylacetoacetate, and silver α-ethylacetoacetate, and an aliphatic primary or secondary amine having 1 to 10 carbon atoms, and a substrate with a surface on which a metallic silver layer which is formed by heating the silver ink composition is provided. According to the invention, it is possible to obtain a silver ink composition suitable for forming a metallic silver layer which has superior glossiness and specularity, and a substrate with a surface on which a metallic silver layer is formed using the silver ink composition.