Using a self-assembly process, we fabricated ordered chains of transparent polystyrene microspheres that have 30°- and 60°-branched structures and that act as coupled-resonator optical waveguides (CROWs). We then observed the optical properties of propagation light through the CROWs. The light spectra were directly measured by guide-collection-mode near-field scanning optical microscopy (NSOM) techniques. The spectrum of light propagating to the 60°-branch shows some sharp peaks, which seem to be associated with whispering gallery modes (WGMs). On the other hand, the spectrum of light propagating to the 30°-branch shows rather broad peaks. Moreover, we observed the detailed structures of the CROWs by high-resolution scanning electron microscopy (HR-SEM), and performed a finite-difference time-domain (FDTD) simulation to explain the NSOM spectra. The results suggest that the microspheres’ branching chains themselves have a light-splitting function, which is a kind of wavelength-selective filter.