AbstractTwo bichromophoric systems (3 and 4) are studied that contain an electron donor (D) and an electron acceptor (A) moiety interconnected by a fully rigid, saturated hydrocarbon‐bridge. In both the shortest through‐bond pathway from D to A has a length of 8 sigma‐bonds, but whereas this path has an all‐trans configuration in 3, two cis elements have been introduced in 4. Photoinduced, intramolecular electron transfer from D to A occurs more than an order of magnitude faster across the stretched all‐trans bridge in 3 than across the bent bridge in 4 notwithstanding the smaller spatial distance in t