The work aims to propose an electrostatic spray method for preparing superhydrophobic surfaces to achieve oil-water separation. The SiO2 particles were sprayed onto the stainless steel mesh surface by electrostatic spray method to construct the rough microstructure, and the surface energy of the SiO2 microstructure was reduced by flusilane. The effects of different electrostatic spraying voltage, spraying time, SiO2 particle size, solution pH and immersion time on surface microstructure and hydrophobicity were discussed. The surface morphologies of the samples were characterized by scanning electron microscope. The contact angles of superhydrophobic stainless steel mesh were measured by contact angle meter to evaluate hydrophobicity. Oil-water separation experiment was conducted by superhydrophobic stainless steel mesh to test the oil-water separation capacity. The SiO2 particles sprayed on the surface of stainless steel mesh could form uniform microstructures. The contact angle of the superhydrophobic mesh obtained by spraying 25 nm SiO2 particles under 6 kV voltage reached 161°. The contact angle was still greater than 150° after immersion in different pH solutions for 15 days, and greater than that of the untreated stainless steel mesh after 35 days. The mesh could collect more than 97% diesel and kerosene, 90% gasoline and tea oil from water, and it could retain rough microstructure and high oil-water separation after 20 times. Superhydrophobic surface can be prepared simply and efficiently by electrostatic spray method, and it has good chemical durability, effective oil-water separation ability and broad application prospects.