Recently, superconductivity has been discovered in rock-salt structured binary lanthanum monoxide LaO through state-of-the-art oxide thin-film epitaxy. In this work, we reveal that the normal state of superconducting LaO is a Z2 nontrivial topological metal, where the Dirac point protected by the crystal symmetry is located around the Fermi energy. By analysing the orbital characteristics, we show that the nature of the topological band structure of LaO originates from the intra-atomic transition from the outer shell La 5d to the inner shell 4f orbitals driven by the strong octahedral crystal-field. Furthermore, the appearance of novel surface states unambiguously demonstrates the topological signature of LaO superconductor. Our theoretical findings not only shed new light into the understanding of the exotic quantum behaviors in LaO superconductor with intimate correlation between 4f and 5d orbitals in La, but also provide an exciting platform to explore the interplay between nontrivial topology and superconductivity.