In the realm of oil-water separation technologies, membrane-based separation emerges as an efficacious approach. Nevertheless, crafting a hydrophilic membrane capable of effectively segregating herbal volatile oil remains a formidable challenge. Our study introduces a facile in situ assembly strategy for fabricating a double-crosslinked composite coating comprising phytate (PA)-polyethyleneimine (PEI) polyelectrolyte complexes and PA-Fe3⁺ assemblies. The PA within the PA-PEI/Fe3⁺ coatings form a double cross-linking layer through interactions with amine groups and metal ions, thereby enhancing interfacial interactions and structural integrity of the membranes. Consequently, the resultant PVDF/PA-PEI/Fe3⁺ membranes exhibit improved coating stability, pronounced hydrophilicity, and exceptional antifouling capabilities, rendering them highly suitable for the separation of diverse herbal volatile oil-in-water emulsions. Furthermore, they possess the capability for reuse with an average retention ratio exceeding 90% and a pure water flux reaching up to 3200 L·m⁻2·h⁻1. Additionally, they demonstrate long-term stability and resistance to corrosion. With a simplistic yet efficient preparation process, the PVDF/PA-PEI/Fe3⁺ membrane holds significant potential for the extraction of oils from herbal volatile oil-in-water emulsions.