Neoteric “Z-pins like” vanadium0.9-silicon0.1 rods (V0.9-Si0.1 rods) as polybasic multiphase oxide compensators were prepared to improve the anti-ablation of C/C-ZrC-SiC over 2500 °C. The microstructure and improvement effect on the anti-ablation of different C/C-ZrC-SiC surface were investigated. Results show that the density of “Z-pins like” V0.9-Si0.1 rod was effectively improved after adding Si. When ablation time was less than 180 s, “Z-pins like” V0.9-Si0.1 rods perpendicular to non-woven cloth layer presented the best improvement of the anti-ablation performance by liquid/gaseous multicomponent oxide compensation. However, when ablation time was greater than 180 s, “Z-pins like” V0.9-Si0.1 rods perpendicular to non-woven cloth layer increased another harm that weaken the anti-ablative performance of C/C-ZrC-SiC, namely, the corrosion damage of oxide layer on the matrix surface caused by excessive oxide melt. Therefore, there is a best improvement of the anti-ablation performance of “Z-pins like” V0.9-Si0.1 rods parallel to non-woven cloth layer.