Ultrafiltration membrane separation technology is considered an effective method for separating oil-water emulsions. However, oil droplets can easily deposit on the surface of the membranes, leading to severe fouling and a decrease in flux. In this study, poly (ethylene oxide)/acrylamide/sodium alginate (PEO/AM/NaAlg) hydrogel nanofibers were deposited on a poly (hydroxybutyric acid) (PHB) electrospun nanofibrous membrane. Subsequently, superhydrophilic (ethylene oxide)-poly(acrylamide)/calcium alginate hydrogel nanofiber composite filtration membranes (PEO/PAM/CaAlg-PHB) were prepared by polymerization and Ca2+ cross-linking using a PHB electrospun nanofibrous membrane as the matrix. The morphology, tensile strength, water contact angle, and oil–water emulsion separation properties of the PEO/PAM/CaAlg-PHB hydrogel filtration membrane were investigated. The results showed that the PEO/PAM/CaAlg-PHB membrane had good anti-fouling performance, with a tensile strength of 1.95 MPa. After 3 h of the filtration operation, the stable flux and oil–water emulsion rejection of the membrane reached 2925.2 L m−2 h−1 bar−1 and 98.66 %, respectively. The preparation method was simple, cost effective, and environmentally friendly, without introducing any organic pollutants. The PEO/PAM/CaAlg-PHB hydrogel filtration membrane shows promise for separating oil–water emulsions.