Nowadays, as the rapid development of portable electronics, wearable electronics, LEDs, microelectronics, and bio-electronics, the fabrication of metallic circuits onto polymer substrates with strong adhesion property is an ever-attracting challenge. In this study, the high resolution and well-defined metallic circuits was successfully prepared on the polymer surface via laser direct structuring (LDS) based on copper hydroxyl phosphate [Cu2(OH)PO4], and the key mechanism of the selective metallization was systematically investigated. XPS confirmed that, after 1064 nm NIR pulsed laser irradiation, the Cu0 (elemental copper) was formed through photochemical reduction reaction of Cu2(OH)PO4. During the electroless plating, because it is the important active catalytic center, this newly formed Cu0 was the key factor to achieve the successful selective metallization. SEM revealed that, after the electroless plating, the copper layer actually physically anchored into the polymer substrate, giving an excellent mechanical adhesion property of the obtained metallic patterns. In addition, the micro-Raman surface imaging approved the generation of the amorphous carbon on the polymer composites surface after NIR laser irradiation, and the chemical reaction region caused by the pulsed laser spot was found approximately at 40 μm. This environmental-friendly and effective strategy for fabricating circuit patterns on the polymer surface has a possible application in the printed circuit plate (PCB) industry.