For the development of high-performance laser protective coatings, this work innovatively proposes the idea of recombining PCS ablative coatings on the surface of traditional yttrium stabilized zirconia (YSZ) thermal insulation coatings. Based on characteristics of the consumption of large amount laser energy through decomposition of polycarbosilane (PCS) and production of high-temperature ceramic protective phases, NiCrAlY/YSZ/PCS-TiO₂ (YPT) and NiCrAlY/YSZ/PCS-Y₂O₃ (YPY) coatings were prepared on the surface of Ni-based alloy by slurry method combined with atmospheric plasma spraying (APS). Based on the effect of TiO₂ and Y₂O₃ addition on the pyrolysis behavior of PCS, the laser ablation resistance of YPT and YPY composite coatings on 10.6 μm CO₂ laser were systematically studied and compared with that of single layer YSZ coating. The results show that YPY and YPT composite coatings have better laser protection effect than traditional YSZ coating, because in the early stage of laser ablation, the PCS decomposition on the coating surface can consume laser energy, and the residual Y₂SiO₅, SiC and SiO₂ phases after ablation can be deposited on the YSZ coating, forming a dense protective layer, which can continue to play a role in laser protection of the YSZ coating. YPY coating has better laser protection performance than YPT coating, because Y₂O₃ has higher thermal conductivity and lower coefficient of thermal expansion. Smaller temperature gradient can be produced in YPY coating, which can alleviate thermal stress. Moreover, Y₂O₃ participates in the pyrolysis of PCS to generate Y₂SiO₅ phase, which inhibits more volume expansion in PCS pyrolysis than that in TiO₂. In addition, the core ablation temperature of YPY coating is higher, and the formation of PCS pyrolysis products SiC and SiO₂ phase is faster, which can timely protect the lower coating, showing better laser ablation resistance. This study is expected to provide a new idea for the design of novel laser resistant composite coatings.