The atomic structure of LiNbO3(0001) surface was investigated by low-energy neutral scattering spectroscopy (LENS). Poled stoichiometric LiNbO3 (SLN) samples were prepared for the measurements. The LENS was developed for surface structure and composition analysis particularly of highly insulating materials and was successfully applied to the structure analysis of the SLN(0001) surface. The polar angle dependences of intensity of scattered He0 from the poled SLN surfaces indicate obvious differences between the negatively and the positively charged surfaces. It is suggested that O atoms cover the surfaces, and the first metal layers underneath the O layer consist of Li and Nb for negatively and positively charged surfaces, respectively, parallel to the applied electric field.