Nitroxide-mediated polymerization (NMP), being a reversible deactivation radical polymerization (RDRP) technique, has been the subject of considerable attention in polymer science. Lavishly granting access to well-defined and highly functional polymers, NMP has paved a huge avenue for complex macromolecular architectures. This book chapter highlights these structures prepared by NMP comprising linear as well as non-linear topologies. The different synthetic approaches relevant to these topologies are outlined, giving a broad overview of the potentialities of NMP in advanced polymer synthesis.