Multi-phase vertically aligned nanocomposite (MP-VAN) thin films represent a promising avenue for achieving complex multifunctionality, exploring novel interfacial phenomena, and enabling complex metamaterial designs and exploration. In this study, a novel self-assembled all-oxides three-phase VAN system was conceptualized and fabricated utilizing pulsed laser deposition (PLD) with a single composite target. Detailed microstructural analysis reveals the presence of three distinct phases: LiNbO₃, CeO_2–x, and LiNbCe_1–xO_y within the MP-VAN films. Subsequently, ferroelectric, dielectric, optical anisotropy, and magnetic properties were systematically investigated to showcase the multifunctionality inherent in these films. This work presents a pioneering approach to designing and realizing MP-VAN systems, and opens up opportunities for tailoring the complex three-dimensional (3D) physical properties and property coupling of VAN films towards diverse device applications.