Polymers are attractive materials for optical waveguide applications due to their low cost, easy processibility and good flexibility. One of the highest priorities in the improvement of polymer optical waveguides is to develop new polymer materials possessing low optical loss, thermal stability, and refractive index controllability. Here, we present promising optical waveguide materials, i.e. calixarene polymers, which possess good optical and thermal properties. Calixarene polymer optical waveguides showed low optical loss (less than 1 dB/cm at 1.3 μm) and good thermal stability (5 wt% loss temperature: higher than 300°C). The control of refractive index of calixarene polymers was also achieved by copolymerization of calixrene with other comonomer. Calixarene molecules are originally known as an inclusion compound in host-gesut chemistry, which can bind various metal ions and organic molecules. Thus, we also investigated the binding property of calixarene polymer against trivalent europium(Eu3+) complex which possesses excellent luminescent characteristics. An interaction, i.e. coordination structure, is established between calixarene polymer and Eu complex, which results in an effective suppression of concentration quenching of Eu complex.