A key curiosity in polymer chemistry is how the principles of small-molecule organic chemistry scale to macromolecules. The ultimate expression of this is at the fine microstructural level, i.e., monomer sequence. As a small foray in this space, I investigated the synthesis of larger sequence-defined polymers by reversible addition-fragmentation chain transfer (RAFT) single unit monomer insertion (SUMI). RAFT SUMI was particularly of interest to this end given its direct analogy to the famous polymerisation method, serving as a direct link between small-molecule and polymer chemistry. Challenges associated with synthesising larger sequence-defined polymers were addressed in two ways. In the first instance, a technical solution was found, whereby solid-phase synthesis was applied to a RAFT SUMI setting. Then, fascinating interplay of remote functional group effects were discovered as a conceptual inversion of standard RAFT chemistry. Interestingly, the latter serves as an example where not only can small molecule organic chemistry inform polymer chemistry, but vice versa.