Vibration spectral properties and dehydration behaviors of goethite nanorods with diameters ranging from 13 to 32 nm were investigated using infrared spectroscopy, thermogravimetric analysis, and X-ray diffraction. All goethite nanorods were highly hydrated with physisorbed and chemisorbed water. As the diameters of goethite nanorods increased, the hydroxyl deformation vibration in the a-b plane showed a significant blue shift, while the Fe-O vibration in the a-b plane shifted to lower frequencies, indicating an enhancement of O-H bond and the ionicity of Fe-O in a-b plane. The hydrated goethite nanorods are also proved to be useful in environmental remedy because of their excellent removal ability of heavy metal ions.