Recently developed sequential reversible addition–fragmentation chain transfer (RAFT) polymerization protocols allow the rapid, fully unattended preparation of quasi-block copolymer libraries that cover a wide range of copolymer compositions in an automated synthesizer. This contribution explores the scope and limitations of this sequential approach for the synthesis of higher order quasi-multiblock copolymers (including copolymer sequences of BAB, CBABC, ABC and ABCD). These syntheses illustrate the utility of this high-throughput approach for the one pot synthesis of functional polymers of increased complexity. Additionally, the use of this experimental technique for method development is highlighted.