A new β-cyclodextrin/graphene oxide hybrid material prepared via a chemical covalent interaction and layer-to-layer assembly was developed as a sorbent for the solid-phase microextraction of fragrance allergens. As a result of its ultra-large surface area, large delocalized π-electron system and abundant hydroxyls, the β-cyclodextrin/graphene oxide-coated fiber could be used to extract particular compounds via strong π–π interactions, van der Waals forces and hydrogen bonding interactions. β-Cyclodextrin with a hydrophobic interior cavity and hydrophilic peripheral face was conducive in extracting the fragrances with hydrophobic and hydrophilic groups. Under the optimized extraction and desorption conditions, the β-cyclodextrin/graphene oxide-coated fiber showed acceptable extraction efficiency for hydrophilic and hydrogen-bonding-donating alcohols. Compared with other methods based on different coating fibers, the proposed fiber obtained wide linear ranges for fragrances with correlation coefficients ranging from 0.9921 to 0.9970, and low limits of detection in the range of 0.050–0.150 μg L⁻¹. The obtained results indicated that the newly developed fiber was a selective, feasible and cost-effective microextraction medium and could be successfully applied for the determination of several fragrances in personal products.