With fiber optical telecommunication systems penetrating into metropolitan and access networks, planar waveguide technology is increasingly being considered a solution to the bottleneck of cost-effective manufacture of passive components. Being recognized for their high thermo-optical coefficient, ease of fabrication, cost-effectiveness, good compatibility with other materials, polymer as a platform technology for waveguide devices is gaining more and more commercial acceptance. Fully exploiting the potentials of the polymeric materials demands comprehensive understanding of both the specific device applications and various polymer systems. The right choice of materials is often the key to the success of component development. Unfortunately, since extensive study on polymeric materials and devices operating at 1.55 micrometer just began recently, few ideal materials have been so far made commercially available. From the polymer chemistry point of view, it is possible to tailor the materials meeting specific and strict requirements for optical waveguide devices. The present author reviews the most promising fluorinated polymers and silicone resins and their demonstrated device applications. The paper is designed for providing guide to both polymer scientists, who want to develop novel high performance materials for waveguide applications, and optical engineers who need to gain insight of the materials.