It is still a big challenge to prepare polymer/layered double hydroxide (LDH) composites with high performance, due to the strong agglomeration tendency of LDHs in the polymeric matrix. In this study, to avoid the agglomerated situation, the orientated LDH nanosheets were vertically grown on a ramie fabric surface, which was then embedded in unsaturated polyester resin (UPR) through the combination method of hand lay-up and vacuum bag. Due to the increased contact area and the restricted interfacial slip in the in-plane direction, the hierarchically LDH-functionalized ramie fabrics (denoted as Textile@LDH) significantly enhanced the mechanical performance of UPR composites. Then, the phosphorus- and silicon-containing coating (PSi) was used for the further improvement of the interfacial adhesion. The tensile strength of UPR/Textile@LDH@PSi composites increased by 121.67%, compared to that of neat UPR. The reinforcement mechanism was studied through analyzing the surface nano/microstructure and wetting properties of the raw and modified textiles, as well as the interfacial interaction between the ramie fabrics and UPR. Meanwhile, the thermal stability, thermal conductivity, and flame-retardant performance of ramie-reinforced UPR composites were improved. Particularly, as-prepared hierarchical Textile@LDH@PSi inhibited the heat release during the combustion process of fabric-reinforced UPR composites, and the peak heat release rate and total heat release values decreased by 36.56 and 47.57%, respectively, compared with the neat UPR/Textile composites. The suppression mechanism was further explored by analyzing the microstructure and chemical compositions of char residues. This research paved a feasible solution to improve the poor dispersion of LDHs in polymers and prepared the high-performance UPR composites with multifunctional applications.