Multiblock copolymers (MBCs) are an emerging class of synthetic polymers that exhibit different macromolecular architectures and behaviours to those of homopolymers or di/triblock copolymers. Owing to the rapidly expanding field of synthetic methodologies applied in the field of polymer chemistry, sequenced controlled MBCs are becoming the new functional materials of this decade. MBCs can now be synthesised with precision and control unlike before and yet some of the synthetic limitations remain a challenge. In this review article, we summarise the various synthetic methodologies that have been reported to date with recent advances in different polymerisation techniques and applications. Multiblock copolymers (MBCs) are an emerging class of synthetic polymers that exhibit different macromolecular architectures and behaviours to those of homopolymers or di/triblock copolymers.