Artificial superlattices, constructed from atomic layers such as graphene using layer-by-layer periodic stacking or sequential epitaxial growth, have emerged as a versatile platform for developing new materials with properties surpassing the existing materials1–3. However, the explored superlattices are predominantly van der Waals (vdW) superlattices, constrained by weak interface coupling4,5. Here we present an efficient synthetic protocol that achieves a family of non-vdW superlattices of carbides and carbonitrides, featuring hydrogen bonding between layers through a stiffness-mediated rolling-up strategy. The crucial step involves customizing the bending stiffness of the atomic layers derived from MAX phases by creating metal vacancies in MX slabs, triggering their ordered rolling-up under rapid flexural deformation. Unlike vdW superlattices, our non-vdW superlattices with hydrogen bonding afford robust interlayer electronic coupling with highly concentrated charge carriers (1022 cm−3). Consequently, our superlattices exhibit a notable electrical conductivity of about 30,000 S cm−1, which is around 22 times that of the counterparts. When used in electromagnetic interference shielding, the optimal non-vdW superlattice film demonstrates a remarkable shielding effectiveness of 124 dB, surpassing that of any known synthetic materials with comparable thickness. The non-vdW superlattices are anticipated to markedly broaden the material platform, offering variable compositions and crystal structures for new developments in artificially stacked systems.
