The elimination of Pb2+ and recovery of lead metal during the treatment of industrial sewage is an important research topic. Montmorillonite (Mnt) is a promising material in this regard. The purpose of the present study was to improve the Pb2+ adsorption ability of Na-containing Mnt (Na-Mnt) by pillaring titania (anatase) into its interlayer spaces using a sol-gel method. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The ratio of Ti to Mnt affected the crystal phase of titania-pillared Na-Mnt (Ti-Mnt), and changed the interlayer spacing of the (001) plane of Ti-Mnt and the growth of anatase. The Pb2+-adsorption capabilities of Ti-Mnt were tested using an aqueous solution of lead nitrate as a wastewater model. The Ti-Mnt prepared adsorbed >99.99% of the Pb2+; leached and activated Ti-Mnt adsorbed >95.7% of the Pb2+, indicating that Ti-Mnt could be recycled effectively. Furthermore, the Pb2+-adsorption capability of Ti- Mnt was related to the interlayer spacing of Mnt, the distribution of anatase particles pillared in Mnt, and the specific surface area, especially with respect to the relationship between the anatase particles and the interlayer spacing of the (001) plane.