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Arsole-containing conjugated polymers are a practically unexplored class of materials despite the high interest in their phosphole analogues. Herein we report the synthesis of the first dithieno[3,2- b;2′,3′- d]arsole derivative, and demonstrate that it is stable to ambient oxidation in its +3 oxidation state. A soluble copolymer is obtained by a palladium-catalyzed Stille polymerization and demonstrated to be a p-type semiconductor with promising hole mobility, which was evaluated by field-effect transistor measurements. [ABSTRACT FROM AUTHOR]