• One-step derivatization and TC-VA-LLME-SFDES method was developed. • Hydrophobic DESs were used as both reducing agent and extraction solvent. • Only 2 min was needed for derivatization and extraction process. • The method was applied for analysis of total Fe in water and food samples. • The method opened up the application of solid DESs in LLME technique. In our work, hydrophobic thymol-based deep eutectic solvents (DESs) with strong reducibility, a lower density than water, and a slightly higher melting point than room temperature were synthesized. Based on these solid DESs, one-step derivatization and temperature-controlled vortex-assisted liquid-liquid microextraction based on the solidification of a floating DES (TC-VA-LLME-SFDES) via UV–Vis spectrophotometry for the rapid determination of total iron was developed. The derivatization and TC-VA-LLME were carried out simultaneously by the addition of DES as both the reducing agent and extraction solvent. After optimization, the calibration curve (5–250 μg L−1, R2 = 0.9982), limit of detection (1.5 μg L−1), limit of quantitation (5.0 μg L−1), precision (≤4.0%) and enrichment factor (92) was obtained. This method was applied for the determination of total iron in water and food samples with satisfactory recoveries (85.4–106.2%). One-step derivatization and TC-VA-LLME only required 2 min. Furthermore, this method opened up the application of solid DESs in liquid–liquid microextraction. [ABSTRACT FROM AUTHOR]