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Recently, metallization on polymer substrates has been given more attention due to its outstanding properties of both plastics and metals. In this study, the metal oxide composite of copper?chromium oxide (CuO· Cr2O3) was incorporated into the polymer matrix to design a good laser direct structuring (LDS) material, and the well-defined copper pattern (thickness =10 ?m) was successfully fabricated through selective metallization based on 1064 nm near-infrared pulsed laser activation and electroless copper plating. We also prepared polymer composites incorporated with CuO and Cr2O3; however, these two polymer composites both had very poor capacity of selective metallization, which has no practical value for LDS technology. In our work, the key reasons causing the above results were systematically studied and elucidated using XPS, UV?vis?IR, optical microscopy, SEM, contact angle, ATR FTIR, and so on. The results showed that 54.0% Cu2+ in the polymer composite of CuO·Cr2O3 (the amount =5 wt %) is reduced to Cu0 (elemental copper) after laser activation (irradiation); however, this value is only 26.8% for the polymer composite of CuO (the amount =5 wt %). It was confirmed that to achieve a successful selective metallization after laser activation, not only was the new formed Cu0 (the catalytic seeds) the crucial factor, but the number of generated Cu0 catalytic seeds was also important. These two factors codetermined the final results of the selective metallization. The CuO·Cr2O3 is very suitable for applications of fabricating metallic patterns (e.g., metal decoration, circuit) on the inherent pure black or bright black polymer materials via LDS technology, which has a prospect of large-scale industrial applications.