AbstractThermoplastic, phase-segregated multiblock copolymers (MBC) with shape–memory capability consisting of poly(ε-caprolactone) (PCL) switching segments and poly(p-dioxanone) (PDO) or poly(ω-pentadecalactone) (PPD) hard segments were prepared on a scale of several kilograms following a newly developed upscaling procedure. Dihydroxytelechelic poly(ether)esters were coupled by an aliphatic diisocyanate gaining products of sufficiently high molecular weights. The obtained biodegradable MBC exhibited good elastic properties and a shape–memory effect (SME) with a switching temperature (Tsw) around body temperature. The yield of the synthesis could be improved and reaction time reduced, while mechanical and shape–memory properties were not affected. These multifunctional materials, which are now available in a larger scale have a high application potential as smart implant materials especially for minimally invasive surgery.