Sulfur hexafluoride (SF6) is known as one of the most powerful greenhouse gases in the atmosphere. Reductive photodegradation of SF6 by styrene has been studied with the purpose of developing a novel remediation for sulfur hexafluoride pollution. Effects of reaction conditions on the destruction and removal efficiency (DRE) of SF6 are examined in this study. Both initial styrene-to-SF6 ratio and initial oxygen concentration exert a significant influence on DRE. SF6 removal efficiency reaches a maximum value at the initial styrene-to-SF6 ratio of 0.2. It is found that DRE increases with oxygen concentration over the range of 0 to 0.09 mol/m3 and then decreases with increasing oxygen concentration. When water vapor is fed into the gas mixture, DRE is slightly enhanced over the whole studied time scale. The X-ray Photoelectron Spectroscopy (XPS) analysis, together with gas chromatography-mass spectrometry (GC-MS) and Fourier Transform Infrared spectroscopy (FT-IR) analysis, prove that nearly all the initial fluorine residing in the gas phase is in the form of SiF4, whereas, the initial sulfur is deposited in the form of elemental sulfur, after photodegradation. Free from toxic byproducts, photodegradation in the presence of styrene may serve as a promising technique for SF6 abatement.