Abstract: The invention relates to a transition metal living free radical and/or atom transfer polymerisation process comprising the steps of: (a) mixing (i) a transition metal living free radical and/or atom transfer radical catalyst, (ii) a plurality of polymerisable monomers, and (iii) an initiator comprising a transferable atom or group a to an amide group to form a mixture; (b) incubating the mixture at a first temperature; and then (c) raising the temperature of the mixture to a second temperature to allow polymerisation of the monomers to proceed to produce polymer. Products and initiators are also provided.