AbstractSummary: Three polymers consisting of alternating perylene bisimide chromophores and flexible polytetrahydrofuran segments of different length have been studied using absorption and (time‐resolved) photoluminescence spectroscopy. In o‐dichlorobenzene, the chromophores self organize to form H‐like aggregates. The photoluminescence spectra of the self‐organized polymers consist of vibronically resolved monomeric perylene bisimde fluorescence (λmax = 538 nm, τ = 3.9 ns) and unstructured excimer‐type emission (λmax = 635 nm, τ = 17 ns). An additional short‐lived (τ ≈ 2 ns) luminescence component is observed and ascribed to the dynamic deactivation of the monomeric photoexcited state via excimer formation or energy transfer.Structure of alternating perylene bisimide – polyTHF copolymers.imageStructure of alternating perylene bisimide – polyTHF copolymers.