A method for manufacturing a substrate with a metal film includes preparing an insulative substrate having the first surface and the second surface on the opposite side of the first surface, forming in the insulative substrate a penetrating hole having the inner wall tapering from the first surface of the insulative substrate toward the second surface, forming a layer of a composition containing a polymerization initiator and a polymerizable compound on the inner wall of the penetrating hole, irradiating the layer of the composition with energy such that a polymer is formed on the inner wall of the penetrating hole, applying a plating catalyst on the polymer, and forming a plated-metal film on the inner wall of the penetrating hole.