A series of thiazole-fused benzothiadiazoles were designed and synthesized, and their structural, electrochemical, and photophysical properties were analyzed. The observed high solubility, in combination with desirably high levels of electron-accepting ability and planarity in the solid state, promises great potential for the application of these compounds as pi-electron-accepting building blocks in organic electronic materials. In addition, the two-dimensional expansion of pi conjugation through the fused thiazole moiety renders these compounds ideal candidates for use as T-shaped pi-conjugation junctions.