Despite ongoing challenges, ablative thermal protection systems are among the most promising methods for safeguarding spacecraft during re-entry thermal protection systems (TPS). A novel aluminium titanate (Al2TiO5/AT) and a highly efficient thermal barrier of coating (TB/TBCs) made from yttria-stabilized zirconia (YSZ), powder, but deposited using the plasma spray technique on polyacrylonitrile (PAN)-based carbon fiber fabric(C)-reinforced with resorcinol phenol formaldehyde resin (RF) composites (C-RF)) would be a potential candidate for TPS applications. This study investigates the composites with varying wt.% of AT that were developed, namely 0 wt.% (YSZ-C-RF), 1 wt.%, 3 wt.%, and 5 wt.% (YSZ-AT-C-RF) by utilizing a hot press moulding machine. Thermal stability and ablation performance of unmodified C-RF with modified YSZ-C-RF and YSZ-AT-C-RF composites are examined through thermogravimetric analysis (TGA) and oxyacetylene torch test/OAT (4.0 MW/m2 for 60 sec). Also, the phase composition and microstructure of the ablated surface are determined by X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. The TBC of YSZ has an obvious influence on the residual weight ratios at high temperatures in C-RF and also plays a positive role in increasing thermal stability under nitrogen atmosphere for enhancing ablation resistance concerning YSZ-C-RF. The mass and linear ablation rates (MAR and LAR) of the composites after modifying the surface by YSZ-coated particles are reduced by 82.98% and 15.65%, respectively. Similarly, the introduction of AT particles and TBC of YSZ results in evidence of improving the thermal stability and the ablation resistance in varying wt.% of YSZ-AT-C-RF composites. The primary optimum AT weight loading for enhancing ablation resistance in YSZ-C-RF composites is 1wt.%. The modification of 1wt.% AT particles and YSZ-Coated particles reduce MAR and LAR by 54.79% and 61.94%, respectively. This work offers a meaningful method to remarkably enhance the ablation performance of the modified C-RF and YSZ-AT-C-RF composites.