In this work, the primer-printed and then self-assembled poly(ethylene terephthalate) (PET) sheets were plated when the bath pH increased from 7 to 11. The effects of bath pH on the structural and electrical properties of electroless nickel plating were investigated systematically using X-ray diffraction (XRD) and scanning electron microscopy (SEM). Results showed that the crystallographic structures of Ni-plated PET (NPP) sheets were face centered cubic, the preferential orientation of the coatings changes from (200) plane to (111) plane, the growth rate of plated nickel coating increased from 3.71[Formula: see text][Formula: see text]m/min to 8.13[Formula: see text][Formula: see text]m/min, the average Ni crystal size was increased from 0.23[Formula: see text][Formula: see text]m to 0.92[Formula: see text][Formula: see text]m, the average EMI-SE of NPP sheets was increased from 37.2[Formula: see text]dB to 38.6[Formula: see text]dB and the surface electrical resistivity of NPP sheets was decreased from 6235[Formula: see text]ohm [Formula: see text] cm to 0.03[Formula: see text]ohm [Formula: see text] cm with the increase of bath pH. The changes in structural and electrical properties were most possibly due to the fact that the thickness of coating increased.