Rhombohedral (ABC)–stacked graphene has emerged as a platform for exploring correlated and topological physics. However, its large-scale, pure-phase synthesis has been hindered by intrinsic thermodynamic metastability and kinetic instability. In this work, we introduce a step geometry–guided epitaxial strategy to deterministically control interlayer slip, enabling the synthesis of pure-phase rhombohedral graphene. Using this approach, we obtained pure (phase purity > 99%) rhombohedral graphene with an area reaching 160 micrometers by 80 micrometers and thickness ranging from ~15 layers to ~120 nanometers. The resulting samples establish the first comprehensive reference dataset of Raman fingerprints and intrinsic band structures from few-layer films to ~200-layer bulk. Electronic transport measurements reveal a layer-antiferromagnetic state and the quantum anomalous Hall effect, enabling scalable exploration of next-generation quantum science and technology applications.