This feature article presents a short review of the recent developments in the synthesis of conjugated polyelectrolytes (CPEs) along with their applications in organic optoelectronic devices with particular focus on the molecular structures of CPEs with ionic functionality, synthetic approaches, and their utilization as an interfacial layer. The orthogonal solubility of the CPEs allows the simple preparation of multilayer organic devices by solution casting on top of a nonpolar organic photoactive layer without disturbing the interfaces, showing their effectiveness in tuning the electronic structures at the interfaces for improving the charge carrier transport and resulting device properties. These achievements highlight the dynamic nature of CPEs and their applicability to a wide range of optoelectronic devices. (C) 2013 Elsevier Ltd. All rights reserved.