The process of optical formation of dielectric waveguiding structures in transparent photopolymerizable composition (PPC) containing non-polymerizable component (NC) is considered. It is shown, that using NC does not break modes of influencing radiation self-channeling, and on the contrary, allows to provide conditions of matching of the synthesized waveguiding structures with optical fibers. Results of computer simulation of nonlinear wave processes in a photopolymerizable medium and experiments on creation of polymeric channels under the influence of laser beams propagating from the face ends of optical fibers in the PPC based OCM-2 with methanol (NC) are presented.