A rapid, simple, sensitive and environmentally friendly method has been developed for the determination of three oestrogens (17β-estradiol (17β-E2), estrone (E1), and diethylstilbestrol (DES)) in milk samples by using vortex-assisted hollow fibre liquid-phase microextraction (VA-HF-LPME) and high performance liquid chromatography. Method is based on the microextraction of oestrogens from sample solution into 15 μL of nonanoic acid as extracting agent, which is placed inside the hollow fibre followed by vortex-mixing. Vortex provided effective and mild mixing of sample solution and increased the contact between analytes and boundary layers of the hollow fibre, thereby enhancing mass transfer rate and leading to high recovery of target analytes. The extraction equilibrium is achieved within 2 min. Parameters influencing the recovery were investigated and optimized. The proposed technique provided good linearity (>0.9984), repeatability (RSD = 2.56–4.38), low limits of detection (0.06–0.17 ng mL−1), and high enrichment factor (330).