The selection of a suitable mediating agent in Reversible Addition-Fragmentation Chain Transfer (RAFT) mediated polymerization is crucial to the degree of control that can be achieved. An overview of work from the Stellenbosch group is presented in which the use of NMR spectroscopy as a tool for evaluating RAFT-agents is highlighted. The occurrence of selective initialization, i.e. the selective conversion of a RAFT-agent into its single monomer adduct is discussed for various classes of monomers, as well as for copolymerization. One of the general rules for living polymerization is that chains should start growing early in the polymerization reaction. Selective initialization is claimed to be the extreme case where all chains have begun growing after the conversion of only one monomer equivalent per RAFT-agent.