The first bulk photopolymerization of multifunctional alkyne and azide monomers using the CuAAC reaction is successfully carried out from low molecular weight, nonviscous monomer resins. Compared to other traditional step-growth bulk photopolymerization, this approach readily provides crosslinked, high glass transition temperature polymers that incorporate triazole linkages throughout the polymer structure with great temporal control.

Christopher N. Bowman and co‐workers report the development of a novel photopolymerization reaction using the copper (I)‐catalyzed azide‐alkyne cycloaddition (CuAAC) reaction to generate polymer networks with unique mechanical properties. The cover image illustrates the formation of a cross‐linked network in the irradiated/light area while unreacted monomer molecules remain in the dark regions.