Sol-gel-processed organic-inorganic hybrid materials combine the merits of inorganic glass and organic molecules, and are therefore a class of materials with good potential for photonics. In this review, two approaches which have shown promising results for producing useful materials for photonics are described: (i) a novel way to fabricate organically doped, multiphasic nanostructured composite monoliths and (ii) a method of fabrication of organically doped, sol-gel-derived optical fibers. For each approach, the preparation process is presented, together with selected applications such as multidye solid-state tunable laser, multiphasic optical power limiter, a micron-scale chemical-sensing and biosensing fibers and solid-state dye-doped fiber lasers.