Thin Ni films were deposited on the (111) surface of YSZ at 1073 K by a pulsed laser deposition technique. The interfacial atomic structure of Ni/YSZ was investigated by high-resolution transmission electron microscopy (HRTEM). It was found that Ni was epitaxially oriented to the YSZ surface, and the following orientation relationship (OR) was observed: (111)_Ni || (111)_YSZ, [110]_Ni || [110]_YSZ. Geometrical coherency of the Ni/YSZ system was also evaluated by the coincidence of reciprocal lattice points (CRLP) method. It was found that the most coherent OR predicted by CRLP method was (705)_Ni || (111)_YSZ, [010]_Ni || [110]_YSZ, which was not consistent with the experimentally observed OR. To understand the detailed atomic structure, HRTEM image simulations were performed. However, simulated images based on both O-terminated and Zr-terminated interface models were quite similar to the experimental image, and thus it was hard to determine which model is comparable with the actual interface only by the HRTEM image simulations. In order to clarify the termination layer at the interface, electronic structures of the Ni/YSZ interface were investigated by electron energy-loss spectroscopy. It was found that significant differences were observed in O-K edge spectra between the interface and the YSZ crystal interior, and the spectrum from the interface showed similar features to the reference spectrum of bulk NiO. This indicates that the Ni-O interaction occurs at the interface to terminate the oxygen {111} plane of YSZ at the Ni/YSZ interface. In addition, the density of Ni-O bonds across the interface in the experimental OR was larger than that in the most coherent OR predicted by CRLP method, which also suggests that the on-top Ni-O bonds stabilize the Ni/YSZ(111) interface.