Abstract Indolo [3, 2-b] indole, containing two fused indole units, is an unexplored but promising electron-rich molecule for constructing donor–acceptor materials due to its planar, symmetric, and extended conjugated structure. We have successfully developed a new synthetic pathway to prepare 2, 7-diboronic ester-indolo [3, 2-b] indole, which was then reacted with dithienodiketopyrrolo-pyrrole acceptor to afford a new acceptor–donor– ...