In this work, the exfoliated and functionalized boron nitride (f‐BN) nanosheets were prepared via facile treatment and used in the intumescent fire retardant (IFR) coatings, which offer passive fire protection to the steel. To acquire the best fire resistance, the formula of the coating was optimized using response surface methodology (RSM) based on central composite design. According to the result, the optimal sample, with 36.2 wt% ammonium polyphosphate (APP), 27.4 wt% pentaerythritol (PER), 16.8 wt% melamine (MEL), and 7.9 wt% f‐BN, was prepared and its fire resistance was tested in our lab. At the end of fire resistance test, the backside temperature of optimal sample was only 185.2°C, which was very close to the RSM‐predicted result, indicating satisfactory fire resistance. During the test, the coating decomposed to form an intumescent char layer with high graphitization degree and compactness, thus suppressing the transfer of heat and protecting the underlying steel. In addition, the optimal coating possessed great water tolerance and thermal stability, and its water contact angle and char yield reached up to 66.7° and 40.5%, respectively. Hence, this IFR coating with satisfied fire retardancy and water tolerance has broad practical future in the fire safety of steel structure.