The peel adhesion between two different electroless-plated Cu layers and polymer substrates was studied. Cu was electroless-plated onto polymer substrates using two different commercial solutions with different compositions. The adhesion strength between the electroless Cu layers and polymer substrates was measured with the 90 degrees peel test. The adhesion was influenced by the coverage, grain size, and the thickness of the electroless Cu layer. Poor coverage of the electroless Cu layer increased the density of the pores at the interface between the Cu layer and the substrates, thereby degrading the adhesion strength because of a decrease in the contact area. In addition, the electroless Cu layers with larger nodules and larger grains were softer and had higher peel adhesion since the soft and ductile Cu layer promoted a greater amount of plastic deformation during the peel test. This led to enhanced peel adhesion. Finally, as the thickness of the electroless Cu layer increased, the peel adhesion decreased. The thicker Cu layers are not easily bent. Poor bending of the Cu layer induced less plastic deformation, causing a decrease in the peel adhesion. In conclusion, soft and thin electroless Cu layers with greater coverage are preferred in order to obtain good adhesion.