Abstract: The ply-dependent thermal anisotropy and power–time coupling effects in Carbon Fiber Reinforced Polymer (CFRP) composites subjected to high-energy laser ablation remain insufficiently understood. In this study, with the laser spot diameter held constant and laser power and irradiation duration taken as variables, laser ablation experiments were conducted on unidirectional, angle-ply, cross-ply, and quasi-isotropic CFRP thin laminates under combined operating conditions. Multi-scale damage characterization was performed using infrared thermography, SEM, and ultrasonic C-scan. A coupled thermal–mechanical numerical model of the laminate was established, incorporating the degradation of interlaminar thermal conductivity with both delamination opening displacement and temperature. The experimental and numerical results indicate that, governed by thermal anisotropy, the temperature fields and damage zones of unidirectional and angle-ply specimens assume elliptical and circular distributions, respectively. The damage characteristic of unidirectional laminates transitions from fibrous protrusion to flame-like morphology at higher power levels. With increasing power density (6.36-25.46 W/mm²) and total energy (1-10 kJ), the laminates exhibit three typical damage modes in sequence: ablation degradation, ablation crater, and ablation hole. This work elucidates the coupled damage mechanism involving laser energy deposition, pyrolysis, and mechanical property degradation, and offers guidance for enhancing the target damage effectiveness of laser weapons.