A series of neutral hexacoordinate silicon(IV) complexes with a SiO4NC or SiO3N2C skeleton was synthesized. Additionally, two neutral pentacoordinate silicon(IV) complexes with a SiO3NC skeleton were synthesized. All compounds studied were structurally characterized by multinuclear NMR spectroscopy in the solid state and in solution and by single-crystal X-ray diffraction. The hexacoordinate compounds studied contain a tridentate dianionic O,N,O or N,N,O ligand, a phenyl ligand, and a symmetrically substituted derivative of an acetylacetonato ligand of the formula type RC(O)–CH=C(OSiMe3)R (R = Me, Ph, CF3). The two pentacoordinate complexes contain a tetradentate trianionic O,N,O,O ligand and a phenyl ligand.