Detecting the Six Polytypes of Five‐Layer Graphite

Graphene layers can assemble in two shifted metastable positions per interface, leading to eight possible structural arrangements in five‐layer graphene, six of which correspond to distinct periodic crystals. These polytypes exhibit diverse symmetries, interlayer electronic hybridization, van der Waals adhesion, and optical responses. Arrangements lacking inversion [I] and mirror [M z ] symmetries host intrinsic polarizations, while those with sufficiently flat electronic bands display orbital magnetization, unconventional superconductivity, and anomalous fractional quantum Hall states. Here, a detailed comparative study of these polytypes is presented, examining their Raman scattering spectra, second‐harmonic optical emission microscopy, and surface electric potential maps. Each configuration is deterministically identified, its natural abundance is quantified, and its relative stability is assessed. Understanding these stacking‐dependent properties is a critical step toward the development of multiferroic devices that leverage sliding transitions between structural configurations.