In this contribution, the current state of the art is summarized and an overview of photoinitiating systems for both radical and cationic polymerizations and their potential application in the preparation of complex linear and cross-linked macromolecular structures are described. Recent relevant studies have been devoted to developing novel free radical and cationic photoinitiators having spectroscopic sensitivity in the near-UV or visible range. Photoinitiated controlled radical polymerization methods leading to tailor-made polymers with predetermined structure and architecture are briefly presented. Several synthetic methodologies for the preparation of epoxy and (meth) acrylate based formulations containing clay or metal nanoparticles are also summarized. The nanoparticles are homogenously distributed in the network without macroscopic agglomeration. Applicability to both free radical and cationic systems is demonstrated.