Poly(p-phenyleneethynylene)s, composed of a rigid backbone with alternating arylenes and ethynylenes, exhibit high conductivity and chemical stability, and thus they have huge potentials for various applications, including chemosensors, electronic and photonic devices. In spite of numerous interesting applications to date, not many researches concerning oligo(p-phenyleneethynylene)s-graft-poly(ethylene oxide)s (OPEs-g-PEOs) have been carried out, let alone their complexation behaviors with carbon nanomaterials. In this article, we present the synthesis of OPEs-g-PEOs and characterize its morphological and spectral properties by various characterization techniques. We have investigated the interaction of OPEs-g-PEOs with single-walled carbon nanotubes (SWNTs) using various characterization techniques, such as UV-visible, photoluminescence, and Raman spectroscopy, along with SEM, TEM, and POM. In this way, we have successfully demonstrated that OPEs-g-PEOs provide a useful means to modify the physical properties of CNTs, especially in terms of their solubility in common organic solvents.