To address the problem of directional selective removal of multilayer composite heterogeneous materials, an integrated processing and detection system based on galvanometer scanning processing and coaxial spectral monitoring was proposed. Combining laser processing and spectral detection technology, aiming at the selective removal of FR-4 multilayer composite copper clad laminate (CCL), the influence rules between material interface and characteristic spectrum, characteristic spectrum intensity ratio and residual rate, spectral signal-to-noise ratio and energy density were systematically explored. The spectral criterion of laser selective processing was established based on the residual rate index, which realizes the patterned precision processing copper layer, and simultaneously realizes the in-situ online analysis and two-dimensional to three-dimensional mapping characterization of the composition and content of the processed materials, the coordinated regulation mechanism of real-time online monitoring and element closed-loop feedback was established.