We report on a rapid and effective method for the determination of methylcyclopentadienyl-manganese tricarbonyl (MMT) in water and gasoline samples. It is based on single drop microextraction using a 2.5 μL drop of the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate. The influence of ionic liquid, volume of the micro-drop, extraction time, ionic strength and volume of sample were investigated. MMT was then quantified by electrothermal atomic absorption spectrometry. The method has a wide linear range (R2 = 0.991), a detection limit (3σ) of 10.0 ng L−1, a standard deviation of 4.8% (for n = 5), an enrichment factor of 124, and gives relative recoveries of 81.2–101.0%. It was successfully applied to the determination of MMT in water and gasoline samples.