Using a simple in situ seeding chemical vapor deposition (CVD) process, comb-like (branched) monolithic CdS micro/nanostructures were grown. Efficient optical coupling between the backbone and the teeth of the branched architecture is demonstrated by distributing light from an UV-laser-excited spot at one end of the backbone to all branch tips. By varying the deposition conditions, the orientation of the branches with respect to the backbone, their size and density can be tuned as well as the size of the backbone. This in situ seeding CVD method has the potential for a low-cost single-step fabrication of high-quality, micro/nanointegrated photonic devices, with tunable complex waveguiding possibilities.