Traditional rigid polyurethane foam (RPUF) with flame retardancy might be easily damaged in some moist condition due to its hydrophobicity, which would lead to unsafety. Therefore, novel surfactants with both hydrophobic fluorinated group and flame-retardant phosphorus group were synthesized. With lower surface tension and more hydrogen bonds formed in polyurethane, the mixed surfactants, which were used in the preparation of RPUF, have not only obviously improved the size uniformity and integrity of cells but also enhanced its hydrophobicity, compressive strength and thermal insulating performance. Besides, effective ‘protection’ could be constructed on the surface of RPUF by prepared surfactants, when ammonium polyphosphate (APP) and expandable graphite (EG) were introduced to provide good flame retardancy. As a result, with just 2.8 wt% content of those functional surfactants, hydrophobic and flame-retardant RPUF with water contact angle of 126 °, limiting oxygen index of 25 %, compressive strength of 1.3 MPa and thermal conductivity of 27 mW/mK, were finally obtained, which is ahead of other flame-retardant RPUF reported before. It's worth noting that, this hydrophobic and flame-retardant RPUF exhibits more stable and durable properties when soaking in HCl solution (2 mol/L), NaOH solution (2 mol/L), NaCl saturated solution and various solvents (THF and EtOH), or under strong fiction for 100 times and high and low temperature cycling test for 20 times. This would provide a novel and effective strategy to endow RPUF with enhanced and durable flame retardancy, hydrophobicity, compressive strength and thermal insulating performance even under extreme conditions.