Diphenyl iodonium hexafluorophosphate salt and N-alkyl morpholino acetophenone were shown to be effective photocatalyst generators for the cross-linking of α,ω-silanol terminated silicone oligomers. These two photoacid and photobase-induced polycondensation pathways provided an attractive and efficient alternative to toxic and expensive organometallic catalysts. The utility of this novel UV-curing process was demonstrated with a combination of time-resolved infrared spectroscopy to follow the fast reaction kinetics and solid-state 29Si nuclear magnetic resonance to investigate the polysiloxane network. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 39875.