A liquid phase microextraction (LPME) method was developed for the determination of sulfur compounds in crude oils and its fractions (e.g diesel). Wide ranges of sulfur compounds including benzothiophene, dibenzothiophene and their derivatives were used as model compounds for extraction. After extraction, the analyses were performed by gas chromatography equipped with sulfur chemiluminescence detector (GC-SCD). Various experiments conditions influencing the extraction such as extraction times, extraction solvents, solvent volume and quantitative parameters were optimized to achieve higher extraction efficiency and high accuracy. The optimized conditions were applied to the determination of sulfur compounds in crude oil and diesel.