The one-pot syntheses of two pentadeca-(15)-block methacrylate-based amphiphilic copolymers, specifically a bipolymer (AB)7A and a quintopolymer (ABCDE)3, are being reported using a fast and easy to scale up procedure that does not require any intermediate purification steps. Both syntheses were carried out using sequential group transfer polymerisation (GTP) and took under 3.5 h. Amino-containing (DMAEMA, DEAEMA), ether (THFMA, MEGMA) and alkyl (EtMA) methacrylates were used to produce the multiblock copolymers with a final Đ < 1.3.