A titania hollow fiber membrane was successfully synthesized in a macro range via a template method coupled with a sol–gel process. Thermal gravimetric and differential thermal analysis (TG-DTA) was employed to study the effect of heat treatment on the synthesized hollow fiber, and the crystal forms of the titania hollow fiber membranes at different temperatures were studied by X-ray diffraction (XRD). The pore structure of the prepared titania hollow fiber was characterized by scanning electron micrograph (SEM) and nitrogen adsorption/desorption measurements. The prepared titania hollow fiber membrane was explored as a new adsorption material for trace metals for the first time and a new method of titania hollow fiber membrane solid phase microextraction (MSPME) online coupled to inductively coupled plasma mass spectrometry (ICP-MS) was developed for the determination of trace amount of Cd, Co, V and Ni in human serum samples. In order to validate the developed method, two certified reference materials of NIES.No.10-b rice flour and BCR No.184 bovine muscle were analyzed and the determined values were in good agreement with the certified values.