Laser-materials interaction is the fascinating nexus where laser optics, physical/ chemistry, and materials science intersect. Exploring the dynamic interaction process and mechanism of laser pulses with materials is of great significance for analyzing laser processing. Laser micro/nano processing of multilayer materials is not an invariable state, but rather a dynamic reaction with unbalanced and multi-scale, which involves multiple physical states including laser ablation, heat accumulation and conduction, plasma excitation and shielding evolution. Among them, several physical characteristics interact and couple with each other, including the surface micromorphology of the ablated material, laser absorption characteristics, substrate temperature, and plasma shielding effects. In this paper, we propose an in-situ monitoring system for laser scanning processing with coaxial spectral detection, online monitoring and identification of the characteristic spectral signals of multilayer heterogeneous materials during repeated scanning removal by laser-induced breakdown spectroscopy. Additionally, we have developed an equivalent roughness model to quantitatively analyze the influence of surface morphology changes on laser absorptivity. The influence of substrate temperature on material electrical conductivity and laser absorptivity was calculated theoretically. This reveals the physical mechanism of dynamic variations in laser absorptivity caused by changes in plasma characteristics, surface roughness, and substrate temperature, and it provides valuable guidance for understanding the dynamic process and interaction mechanism of laser with multilayer materials.