Environmentally-benign electroless nickel–phosphorus (Ni-P) plating technique on acrylonitrile-butadiene-styrene (ABS) substrates was developed. Using the supercritical carbon dioxide as a carrier solvent of catalysis precursor to ABS, the usage of harmful acid could be avoided and the amount of waste water could be reduced. The developed technique consists of three steps: the first step is the hydrophilic modification of ABS in injection molding process, the second is the scCO2-assisted impregnation of the polymer substrate with Pd(hfa)2, and the third step is the electroless plating reaction on the substrate. In the first step, we used an antistatic agent (Sanyo Chemical Ind., Pelestat® NC6321), which is a multi-block copolymer poly(ether-ester-amide)(PEEA). The PEEA and ABS were molded by an injection molding machine to prepare substrates. Exploiting the characteristics of the fountain flow in mold cavity, the PEEA domain was elongated in the flow direction and made rich in the area close to the surface of the molded substrate. In the study, we prepared the ABS/PEEA blend substrates with different blend ratio of PEEA to butadiene and observed the effects of PEEA and butadiene domains on the blend morphology and the adhesiveness of the plated metal to polymer. It was found that the amounts and size of PEEK and butadiene domains near the surface of the molded polymer substrate were key factors of increasing the adhesiveness of the plated metal. When the amounts of PEEA and butadiene domains near the molded surface were increased, the metal-polymer composite layer, which was formed near the surface, was increased. Then, the adhesive strength of Ni-P metal to polymeric substrate increased. As a result, the uniform Ni-P metal film was successfully formed on the ABS/PEEA (95/5) blend with the average adhesive strength of 9 N/cm.