Functional nanoparticles modified silica nanofibrous materials with good flexibility, a hierarchical mesoporous structure, and excellent durability would have broad applications in efficient removal of contaminants, yet have proven to be enormously challenging to construct. Herein, we reported a strategy for rational design and fabricating flexible, hierarchical mesoporous, and robust ZrO2 nanoparticle-embedded silica nanofibrous membranes (ZrO2/SiO2 NM) for phosphate removal by combining the chitosan dip-coating method with the electrospinning technique. Our approach allows ZrO2 nanoparticles to be in situ firmly and uniformly anchored onto SiO2 nanofibers to drastically enlarge the specific surface area and porosity of membranes. Therefore, the resultant ZrO2/SiO2 NM exhibited a prominent removal efficiency of 85% and excellent adsorption amount of 43.8 mg P g(-1) membranes in 30 min toward phosphates. Furthermore, the removal performance toward different types of phosphates revealed that the resultant membranes also could be used to remove phosphates in detergent and fertilizer water samples. More importantly, the membranes with good flexibility could directly be taken out from solution after use without any post-treatment. Such a simple and intriguing approach for fabricating nanofibrous membranes may provide a new platform for constructing membranes with superb phosphate removal performance.