Structural model of ZrO2-doped Li2O–SiO2-based multi-component glass, which is developed as a mother material for high-strength glass-ceramics, is constructed by the molecular dynamics–reverse Monte Carlo (MD–RMC) method based on anomalous X-ray and neutron scattering data. In particular, we have succeeded in extracting reliable local structural information around Zr from the MD–RMC model. It was found that a significant fraction of edge-sharing structural units was formed around Zr–O and Li–O polyhedra, resulting in a densely packed configuration of O atoms. This configuration was manifested by a very sharp principal peak in the neutron scattering data. Our model suggested that both the Zr and Li ions are incorporated in the glass as distorted ZrO6 octahedra and distorted LiO4 tetrahedra, respectively. These structural features are discussed in terms of the crystallization behavior of this material.