The use of dielectric property monitoring to develop an underpinning understanding of the molecular transformations involved in achieving the successful, rapid in situ synthesis of a catalytic chain transfer polymerisation (CCTP) catalyst using microwave heating is reported. The hypothesis behind the molecular design of this catalyst, such that it was tailored towards the application of microwave heating (MWH), is discussed, reviewed relative to the empirical results and compared to the performance of a benchmark preformed catalyst. The overall number/type of function group present in the catalyst, the degree of flexibility exhibited by its organic ligand system and level of solvation achieved are shown to be key factors affecting the interaction between the catalyst and the applied microwave energy. Use of microwave heating leads to fast, in situ formation of the catalyst (approximately 32 s) within the polymerisation mixture, rendering pre-preparation steps unnecessary and ensuring it is generated prior to the polymerisation reaction commencing. Thus potentially presenting an enormous opportunity to intensify current industrial processes.