Integration of oxides with silicon fuses advanced functional properties with a mature technological platform. In particular, direct EuO/Si contact holds high promise for spintronics but requires single‐crystalline epitaxial films with atomically sharp interfaces. The standard approach employing regular 2D superstructures of metal atoms on the Si surface fails to meet the challenge. Here, an alternative route is designed and shown to solve the problem. This route avoids regular templates; the chaotic 2D distribution of metal atoms on the Si surface prevents stabilization of unwanted crystal orientations. Thus, the disordered submonolayer phase at the interface promotes order in oxide/Si coupling, as witnessed by a combination of diffraction techniques and high‐resolution electron microscopy. The results not only mark tangible progress in manufacturing EuO/Si contacts but also provide a general framework for monolithic integration of functional oxides with semiconductor substrates.