In this work, poly(acrylic acid)-based layers were injected to form a sandwich layer between the cationic and anionic species for a compact and effective fire-retardant coating on cotton fabric using the layer-by-layer coating technique. From the SEM analysis, as the number of tri-layers increases, the attachment intensity increases, as can be seen for poly(acrylic acid) chitosan and bentonite clay PCB-5TL (the highest tri-layers), while in the case of halloysite-based coatings, as the number of tri-layers increases, instead of attachment, the agglomeration increases due to the high surface area of halloysite nanoclay tubes. FTIR and UV confirmed the finding from the new peak entry and an increase in thickness. The highest thermal residue, ~18%, was obtained for poly(acrylic acid) chitosan and halloysite nanoclay PCH-5TL with a maximum degradation peak intensity at ~389 °C. From the flammability and after-burning SEM investigation test, it was observed that the halloysite-based coating with a higher number of layers offered higher resistance against the flame spread and ignition and, thus, produced a higher amount of char.