The present study aimed to evaluate the surface etching of the acrylonitrile-butadiene-styrene (ABS) resin in the MnO2-H3PO4-H2SO4 colloid. To enhance the soluble Mn(IV) ion concentration and improve the etching performance of ABS resin, H3PO4 was added as a complexing agent into the MnO2-H2SO4 etching system. The effects of the H2SO4 concentration and etching time on the surface topography, surface roughness, adhesion strength, and the surface chemistry of the ABS substrates were investigated. The optimal oxidation potentials of MnO2 in the colloids decreased from 1.426 to 1.369 V with the addition of H3PO4. Though the etching conditions changed from 70 degrees C for 20 min to 60 degrees C for 10 min, the adhesion strength between the ABS substrates and electroless copper film increased from 1.19 to 1.33 KN/m after etching treatment. This could be attributed to the significant increase of the soluble Mn(IV) ion concentration in the MnO2-H3PO4-H2SO4 colloid. The surface chemistry results demonstrated that the oxidation reaction of -C=C- bonds in the polybutadiene phase was accelerated in the etching process by the addition of H3PO4, and the abundant -COOH and -OH groups were formed rapidly on the ABS surface with the etching treatment. These results were in agreement with the results of surface scanning electron microscopic observations and adhesion strength measurement. The results suggested that the MnO2-H3PO4-H2SO4 colloid was an effective surface etching system for the ABS surface roughness.