Abstract: In order to determine the quality of wastewater from a section of butadiene polymerization, purge and trap, static headspace, solid-phase extraction, solid-phase microextraction and liquid-liquid extraction as pretreatment methods coupled with GC/MS (gas chromatography/mass spectrometry) were used for analysis of the wastewater. In total 16 kinds of volatile and semi-volatile organic compounds were found in the wastewater including alkene, benzenes, organic nitrile, polycyclic aromatics, ethers, alcohols and amines. The concentration of suspend solids (SS) was 540.31 mg/L, while the particle sizes ranged from 0.10-5.00 μm. Its adsorption capacities for xylene, ethylbenzene, styrene, 1,5-cyclooctadiene and other organic matter were 4.83%-33.21%. Significant differences were found between the wastewaters from the butadiene polymerization section and domestic sewage. Fluorescent regions of the former focused on λ_Ex /λ_Em =205-285 nm/310-360 nm, which mainly consisted of five fluorescence peaks λ_Ex /λ_Em =285 nm/350 nm, 260 nm/310 nm, 225 nm/345 nm, 210 nm/315 nm and 230 nm/360 nm. The five peaks were caused by benzenes and polycyclic aromatics such as toluene, indigo, styrene, dehydroabietic acid, fluorene and phenanthrene. UV absorption spectrophotometry focused around 200-250 nm, which was caused by conjugated diolefins, unsaturated aldehydes, ketones, and benzenes such as 1,3-butadiene, benzaldehyde, acetophenone and 4-phenyl-1-cyclohexene.