Block-copolymer-like supramolecules (see Figure) permit thermal tuning of the microphase period due to reversible supramolecular assembly and disassembly. The supramolecular system based on a binary end-functionalized blend forming diblock- and triblock-like supramolecules shows that the lamellar microphase upon heating swells up to almost 300%. Such effective temperature tunability of the microphase period may find a variety of uses in applications that require patterning over large dimensions.