In this paper, a carboxyl-functionalized organophosphorus oligomer was immobilized onto cotton fabrics using 1,2,3,4-butanetetracarboxylic acid as an environmentally-friendly binder, in the presence of sodium hypophosphite, used as a catalyst, and triethanolamine, which contributes to phosphorous-nitrogen synergism. Moreover, with the aim of reducing the formation of insoluble calcium salt during home laundering, due to the free carboxylic acid groups bound to the cotton fabric, the treated samples were recoated employing three sol-gel precursors, namely 3-aminopropyltriethoxysilane, tetraethoxysilane and 3-glycidyloxypropyltriethoxysilane. Samples were thoroughly characterized to understand the bonding between coatings and substrate, as well as the related surface morphology. The thermal behaviour was investigated by thermogravimetric analysis, flame and combustion tests. The results revealed that the treated fabrics were able to achieve self-extinction. Comparing to the untreated sample, tearing strength of PMIDA/BTCA/SHP fabric was reduced in both warp and weft directions, while fabrics coated with an additional sol-gel layer were affected more significantly.