Abstract Few‐layer black phosphorus (FL‐BP) has been intensively studied due to its attractive properties and great potential in electronic and optoelectronic applications. However, the intrinsic instability of FL‐BP greatly limits its practical application. In this study, the amphiphobic FL‐BP is achieved by functionalization of 1H,1H,2H,2H‐perfluorooctyltrichlorosilane (PFDTS) on the surface of FL‐BP. The obtained PFDTS coated FL‐BP (FL‐BP/PFDTS) demonstrates enhanced stability, which is not observed during significant degradation for 2 months in high moisture content environment (95% humidity). Particularly, attributing to the surface amphiphobicity, FL‐BP/PFDTS exhibits strong surface water repellency in the presence of oleic acid (as the contaminant), while other passivation coating layers (such as hydrophilic or hydrophobic coating) become hydrophilicity under such conditions. Owing to this advantage, the obtained FL‐BP/PFDTS demonstrates enhanced stability in high moisture content environment for 2 months, even though the surface is contaminated by oil liquid or other organic solvents (such as oleic acid, CH2Cl2, and N‐methyl‐2‐pyrrolidone). The passivation of FL‐BP by amphiphobic coating provides an effective approach for FL‐BP stabilization toward future applications.