High corrosion resistant Cu-Co-P coatings were firstly prepared on polyethylene terephthalate (PET) substrate by electroless plating in combination with UV/ozonolysis irradiation under optimized cobalt sulfate heptahydrate concentration, pH value, plating temperature and time. The copper polyalloy/PET composite can be obtained in three steps, namely: (i) the generation of oxygen-containing functionalities (carboxylic groups) onto PET surface through UV irradiation combined with ozone, (ii) Cu seeding catalysts were obtained after being immersed into cupric citrate and NaBH4 solutions subsequently, and (iii) Cu-Co-P polyalloy metallization using electroless plating bath. Attenuated total reflection fourier transformation infrared spectrometer (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), water contact angle measurement and energy dispersive X-ray analysis (EDAX) were utilized to track the surface changes during the whole process. The electroless plating conditions were optimized by an orthogonal experiment (L-9(3)(4)) for Cu-Co-P coating as follows: CoSO4 center dot 7H(2)O addition of 0.08 M, pH value, plating temperature and time were set on 10.0, 35 degrees C and 25 min, respectively. Under the optimal conditions, copper polyalloy possessed high adhesive strength and the lowest surface resistance (8.06 Omega/sq), while maintaining reliability even after over 1000 times of bending and mechanical stress. The results of scanning electron microscope (SEM) and atomic force microscope (AFM) measurements showed that Cu-Co-P layer formed on PET surface was imparted with fine uniformity and high compactness. Electrochemical test revealed the optimized Cu-Co-P coatings exhibited high corrosion resistance in NaCI, NaOH and HCI solutions, respectively. The excellent electromagnetic interference shielding effectiveness (EMI SE >99.999% at frequency ranging from 30 MHz to 1000 MHz) of copper polyalloy/PET composites was confirmed by the spectrum analyzer. Therefore, this copper polyalloy will have potential applications in microelectronics packaging and coatings for anti-corrosion and electromagnetic interference shielding. (C) 2017 Elsevier B.V. All rights reserved.