The optical properties of mechanochromic materials change under mechanical stress. Segmented polyurethanes are elastomers composed of amorphous, saturated chain soft segments, and rigid pi-conjugated hard domains. Within aggregates of hard domains pi-pi interactions may form and result in perturbation of the optoelectronic properties of the system. Disruption and restoration of these electronic interactions within the material may lead to observable mechanochromic response. A series of oligothiophene diols and diamines, as well as a naphthalene diimide diol, have been synthesized for incorporation into the hard domains of segmented polyurethanes and polyureas using long poly(tetramethylene oxide) chains as soft segments. The resulting polymers were evaluated to determine their extent of polymerization and their thermal stability. The optical properties of the materials were studied in solution and as thin films. Where possible the electrochemical properties of the polymers were also explored. The length of the soft segment chains in the segmented polyurethanes hindered electronic coupling of hard domains. Future work involving smaller, more solubilizing soft segments may allow for easier material characterization and mechanochromic response. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 4861-4874, 2011