The synthesis and characterization of a series of poly(3-allcyltellurophene)s are described. Polymers are prepared by both electrochemical and Kumada catalyst transfer polymerization methods. These polymers have reasonably high molecular weights (M-n = 5.4-11.3 kDa) and can be processed in a manner analogous to that of their lighter atom analogues. All examples exhibit red-shifted optical absorption, as well as solid-state organization, as evidenced by absorption spectroscopy and atomic force microscopy. Overall, the synthesis and characterization of these materials open up a wide range of future studies involving tellurium-based polyheterocycles.