Metal oxide-based stationary phases are not only viable alternatives to silica-based stationary phases but in many instances and for some purposes are superior to them.In this paper, titanium (ⅣV) n-butoxide is used as a precursor for preparation of fiber for solid-phase microextraction (SPME) by sol-gel technique.In general, titania-based sol-gel reaction is very fast and need to be decelerated by the use of suitable chelating agents.But in the present work, a judiciously designed sol solution ingredient was used to create the titania-hydroxy-terminated silicone oil (titania-OH-TSO) coating without the addition of any chelating agent, which simplified the sol-gel procedure.The possible sol-gel mechanism was discussed and confirmed by IR spectra.The extraction efficiency of the new fiber was evaluated by the determination of aromatic amines, phenols and polycyclic aromatic hydrocarbons.