In this study, LiTi2O4 was synthesized as a possible catalyst in the Li-N-H system. The properties of hydrogen desorption in the Li-N-H system with a homogeneous catalyst have been investigated. The X-ray diffraction and X-ray photoelectron spectroscopy results indicated that the single phase of LiTi2O4 was successfully synthesized and it was stable in the sample after high energy ball-milling and heat treatment. LiTi2O4 exhibited a catalytic effect in the Li-N-H system according to the thermogravimetry differential thermal analysis results. During dehydrogenation, a storage capacity of 5.7 wt % was obtained under moderate temperature. A sharp peak of thermal gas desorption mass spectrometry curve occurred at 227 °C. Furthermore, the catalytic mechanism of LiTi2O4 in the Li-N-H system was discussed in accordance with the experimental results.