In a recent study of aqueous phase methyl tertiary butyl ether (MTBE) adsorption onto hydrophobic molecular sieves, the solid phase micro-extraction gas chromatography analytical technique was used to measure MTBE concentrations in water. The method was especially beneficial in measuring MTBE concentrations in the microg/l range, but anomalies were observed that investigators should be aware of before employing this technique. Specifically, it was observed that the calibration of the extraction fiber with known MTBE concentrations was non-linear over all concentration ranges. The technique was not suited to higher concentrations, and dilutions were necessary to increase the working range of the technique. Lastly, the fiber was observed to extract increasingly less MTBE from known standard solutions over time, requiring repeated calibrations to obtain reliable concentrations of unknown samples.