Mica is a naturally abundant layered silicate mineral that has higher strength than other layered silicate minerals, but its inherent brittleness limits its application in some fields. In this work, mica was ultrasonically exfoliated into a single-layered nanomaterial after thermal activation, acidification, sodium replacement, and cetyltrimethylammonium bromide (CTAB) intercalation and then modified with ureido-pyrimidinone (UPy)-based PEG chains. Vacuum-assisted self-assembly was used to construct supramolecularly modified single-layered mica into bulk materials, in which the mica nanosheets were stacked into mica paper. The reversible quadruple hydrogen-bonded UPy moieties provided a high binding constant and significantly improved the strength and toughness of the obtained mica paper. These force-induced assembled mica papers showed significantly improved tensile strength and toughness compared with pure mica paper and simultaneously maintained the heat resistance of the mica materials, which may be good candidates for the substrates of flexible sensors working at higher temperatures.