Microwave-assisted liquid–liquid microextraction based on solidification of floating organic droplet (MA-LLME-SFO) was first developed and applied to the extraction of triazines in honey samples. 1-Dodecanol, which is of low toxicity, low density and has an appropriate melting point near room temperature, was chosen as the extraction solvent. Furthermore, traditional organic dispersive solvents were avoided in this method with the aid of microwave irradiation. Several experimental parameters, including the type and volume of extraction solvent, microwave power and irradiation time, pH of the sample solution, ionic strength and centrifugation rate were investigated and optimized. The proposed method showed a good linearity within the range of 5.00–250.00 μg kg−1 with the correlation coefficients ranging from 0.9994 to 0.9998. The limits of detection for cyanazine, desmetryn, terbuthylazine and dimethametryn were 1.39, 0.95, 1.20, and 1.07 μg kg−1, respectively. The recoveries of the analytes ranged from 74.84 to 112.74% and the relative standard deviations were lower than 13.10%, when the present method was applied to the analysis of real samples.
