The present invention provides a method of forming a chip with TSV electrode. A substrate with a first surface and a second surface is provided. A thinning process is performed from a side of the second surface so the second surface becomes a third surface. Next, a penetration via which penetrates through the first surface and the third surface is formed in the substrate. A patterned material layer is formed on the substrate, wherein the patterned material layer has an opening exposes the penetration via. A conductive layer is formed on the third surface thereby simultaneously forming a TSV electrode in the penetration via and a surface conductive layer in the opening.