A headspace (HS) solid‐phase extraction (SPE) based on polydimethylsiloxane (PDMS)/ionic liquid (IL) sponge was developed for the extraction of lavender essential oil. The PDMS after loading of 1‐butyl‐3‐methylimidazolium tetrachloroferrate ([BMIM]FeCl4) with a high surface area and excellent adsorption capacity was successfully applied in the SPE process. Microwave distillation (MD) coupled with HS‐PDMS/[BMIM]FeCl4 extraction after GC–MS was proposed. Various experimental parameters were studied. The optimal conditions were as follows: optimal IL, [BMIM]FeCl4; volume ratio of IL to ethanol, 1:5; extraction solvent, n‐hexane; microwave power, 600 W; and irradiation time, 12 min. The limits of detection and quantification of the analytic compounds were in the ranges 4.00–16.32 and 10.00–40.00 ng, respectively. The intra‐day and inter‐day precisions were in the ranges 0.37–1.94% and 1.20–2.45%, respectively. Under the optimized conditions, 13 samples of 3 lavender varieties were analyzed, and 40 compounds were identified. Lavender varieties were distinguished using principal component analysis. The results showed that MD‐HS‐PDMS/IL‐GC–MS is a novel, simple, and sensitive method for the determination of essential oil in complex plant samples.