Micro-patterns created by the excimer laser and activated by reactants for electroless copper plating are described in this paper. The generated micro-patterns are transformed into copper patterns on the substrate and copper microstructures are formed. This method simplifies the manufacturing process of making circuits on boards compared with the conventional lithography process of forming copper patterns on the substrate. Micro-patterns generated by the excimer laser cause changes of surface electric properties and activation selectively. A chemical reaction through these activated areas may deposit metal, such as copper. The KrF excimer laser not only provides simple and fast machining patterns, but also uses its high-energy density to drill holes and circuits directly. Palladium ions are added as mediators in the electroless plating solution to enable a continuous electroless copper deposition. According to the experiment of excimer laser-assisted electroless copper plating, the procedures of pretreatment and post-cleaning are the key factors that resulted in excellent selective plating. The samples were pretreated by sodium dodecyl sulfate (SDS) and post-cleaned by acetone and diluted nitric acid resulting in distinct micro-patterns. The deposition area is confined to the excimer laser-ablated portion resulting in good selective plating.