In this contribution, we report the synthesis of chiral all‐conjugated branched poly(phenylene ethynylenes) with a controlled amount of branching. Subsequently, the self‐assembly of these PPEs is studied by means of UV–vis, fluorescence spectroscopy, and DSC and the influence of branching is investigated. Finally, CD‐spectroscopy is used to study the influence of branching and self‐assembly on the chiral expression of these polymers. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 79–84