Polymeric multimode waveguides are of particular interest for optical interconnections in short-reach data links. In some applications, for example in space-borne systems, the use of advanced materials with outstanding performance in extreme environments is required (temperature and radiation). In this paper therefore, we present novel siloxane polymers suitable for these applications. The materials are used to form straight, 90° bent and spiral polymer waveguides by low-cost conventional photolithographic techniques on FR4 substrates. The samples have been tested to investigate their propagation characteristics and demonstrate their potential for high-speed data links. Overall, there is strong evidence that these multimode waveguides can be successfully employed as high-speed short-reach data links. Their excellent thermal properties, their low cost and the simple fabrication process indicate their suitability for a wide range of space applications.