Acid copper plating has been extensively applied to various fields such as decorative plating and through-hole plating. In addition to these applications, this technology has been utilized for the metalization of small electronic devices since acid copper plating was adapted to the copper damascene process. Under such new trends, the proper assessment of additives, including their controllability and accessibility for a wide variety of demands, has become an urgent issue. Using commercially available acid copper plating processes, we have evaluated these factors for via-filling and for high throwing power. We compared them in terms of changes in the crystal size and grain of the deposited copper, which are known to change with time, and we also evaluated the influence of additives on the hardness and electrical resistivity. It was confirmed that optimization in selecting and quantifying additives enables deposition of a film characteristically comparable to the acid copper plating process with high throwing power even though the process has a special deposition capability like via-filling.