This paper investigates the material removal behavior of diamond/Cu composites by multi-passes infrared nanosecond pulsed laser ablation, focusing on the formed surface cracks, periodic ripples, profile evolution and deposition. Combining nanosecond laser ablation experiments with simulations based on thermophysical properties is then undertaken to effectively reduce the maximum thermal stress and inhibit crack initiation and propagation. Three types of cracks were identified in nanosecond laser ablation, which were influenced by the diverse thermophysical properties of the material and the temperature gradient. The periodic ripples of 300–1800 nm on the sidewalls of the machined groove on diamond grains were induced when the laser fluence approached the ablation threshold, which did not even appear on the copper matrix as the thermal effects dominate. The groove profile showed a limited change as the ablation passes further increase to be over 40 due to the plasma shielding effect inside the groove, the laser defocusing phenomenon and the increased difficulty of sputtering the molten material. In addition, the different ablation mechanisms of diamond and copper resulted in the formation of overlapping deposition layers with changed surface characteristics at varying laser energy densities. The uneven island-like recast layer affected the uniformity of the ablated grooves, which was dependent on the material microstructure and accumulated laser energy.