With the development of femtosecond laser processing technology, and the demand of practical application, it is more and more required that the research and application of femtosecond laser processing technology turn from single system to composite system. In this paper, by studying the ablation crater shape, Raman spectral characteristic peak and micro/nano structure evolution of femtosecond laser processing of double-layer films (DLC/TiN, the Vickers hardness is all greater than 2000 GPa, greater than 40 GPa is called ultrahard material) with pulse number, the femtosecond laser ablation removal rule of double-layer films (DLC/TiN) was discovered, that is, the graphitization modification of the first layer of diamondlike carbon film (DLC/ TIN) would first occur with laser pulse deposition. Then a "mountain dome" shaped bulge is generated, and the bulge is removed at the center, and the ablation crater is generated with nearly linear depth and pulse number, that is, the ablation removal rate of the upper and lower layers is consistent. It can provide important reference for femtosecond laser processing of microholes, microgroove and complex patterns on double-layer films (DLC/TiN), and expands the application of laser.