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Four acceptor–donor–acceptor (A–D–A)-type molecules bearing indacenodithiophene as donating central core and various end-capping acceptor units have been designed and synthesised as <i>n</i>-type materials suitable for organic solar cells (OSCs). The studied optical and electrochemical properties supported by theoretical calculations revealed that the nature and the strength of the terminal groups exert a decisive influence on the polymer bulk-heterojunction OSC performance.