Macro-porous ceria was synthesized by the hard template (nanocasting) method using silica nanospheres as template material. Also, this ceria photocatalyst was used to remove toxic lead ions and methylene blue dye from aqueous solutions by an adsorption and UV-photocatalysis system in sequence. The macro-porous ceria had relatively high BET specific surface area and wide pore size distributions. The macro-pores consisted of spatial gaps generated by aggregates of ceria nanoparticles growing in a branch shape due to the inhibition of crystal growth with the silica nanospheres. X-ray photoelectron spectroscopy (XPS) revealed that the high adsorption performance of the macro-porous ceria is due to the presence of large amounts of surface hydroxyl groups in water. This macro-porous ceria material exhibits higher overall removal performance by the adsorption and UV-photocatalysis than conventional non-porous ceria.