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Inorganic graphene analogues are a conceptually new class of materials that offer new opportunities to satisfy peoples requirement of high-quality large-area uanodevices.This talk summarizes series of novel pathways developed to fabricate the inorganic graphene analogues with layered/non-layered structure as well as the quasi-layered structure1-7.Their fine structure was characterized by X-ray absorption fine structure spectroscopy, and defect structures were characterized by positron annihilation spectrum and electron spin resonance1,5,6.