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UV/EB cationic curing is an alternative radiation curing technology circumventing some of the free radical polymerisation disadvantages like air inhibition and poor adhesion on difficult substrates. Nowadays a number of new commercial photoinitiators, monomers and co-resins suitable for such systems are available. It can be mentioned for example trimethylolpropane oxetane (TMPO) as a non irritant highly reactive diluent as well as new oligomeric photoinitiators. In this paper, we present a number of new polyols acting as chain transfer crosslinkers and flexibilizers as main function. But they also bring other benefits like improved adhesion and rheology of different inks. These benefits are highlighted using different substrates and ink formulations.