Boron nitride nanosheets (BNN) were prepared by molten hydroxide-assisted liquid exfoliation from hexagonal boron nitride powder with an effectively high yield, and then modified with hexachlorocyclotriphosphazene (HCCP) to obtain HCCP-BNN. The series of samples were applied to prepare flame-retardant cotton fabrics with the impregnation-drying method, and successful treatment was confirmed by scanning electron microscopy. The combustion performance of the as-prepared cotton fabrics was tested and evaluated. After coating with HCCP-BNN, the combustion rate of the fabric is reduced in vertical and horizontal combustion conditions and the limiting oxygen-index value of cotton fabric increases to 24.1, becoming less flammable than the blank cotton. The fibrous structure of the BNN and HCCP-BNN coated fabrics is relatively complete after combustion, which indicates that BNN have a certain protective effect on the fabric. The results demonstrate HCCP-BNN as an effective flame-retardant for cotton fabrics.