The availability of graphene and other two-dimensional (2D) materials on a wide range of substrates forms the basis for large-area applications, such as graphene integration with silicon-based technologies, which requires graphene on silicon with outperforming carrier mobilities. However, 2D materials were only produced on limited archetypal substrates by chemical vapor deposition approaches. Reliable after-growth transfer techniques, that do not produce cracks, contamination, and wrinkles, are critical for layering 2D materials onto arbitrary substrates. Here we show that, by incorporating oxhydryl groups-containing volatile molecules, the supporting films can be deformed under heat to achieve a controllable conformal contact, enabling the large-area transfer of 2D films without cracks, contamination, and wrinkles. The resulting conformity with enhanced adhesion facilitates the direct delamination of supporting films from graphene, providing ultraclean surfaces and carrier mobilities up to 1,420,000 cm2 V−1 s−1 at 4 K.

Recently, scalable production of large‐area graphene films on metal foils with promising qualities is successfully achieved by eliminating grain boundaries, wrinkles, and adlayers. The transfer of graphene from growth metal substrates onto functional substrates remains one inescapable obstacle on the road to the real commercial applications of chemical vaport deposition (CVD) graphene films. Current transfer methods still require time‐consuming chemical reactions, which hinders its mass production, and produces cracks and contamination that strongly impede performance reproducibility. Therefore, graphene transfer techniques with fine intactness and cleanness of transferred graphene, and improved production efficiency would be ideal for the mass production of graphene films on destination substrates. Herein, through the engineering of interfacial forces enabled by sophisticated design of transfer medium, the crack‐free and clean transfer of 4‐inch‐sized graphene wafers onto silicon wafers within only 15 min is realized. The reported transfer method is an important leap over the long‐lasting obstacle of the batch‐scale graphene transfer without degrading the quality of graphene, bringing the graphene products close to the real applications.