A hydrophilic polyfluorene-based conjugated polyelectrolyte (CPE) Poly[9,9-bis(4′-(6″-(diethanolamino)hexyloxy) phenyl)fluorene], PPFN-OH (Scheme 1) has been synthesized and utilized as cathode interlayer for both polymer light emitting diodes (PLEDs) and solar cells (PSCs). For comparison, another CPE namely Poly[9,9-bis(6′-(diethanolamino)hexyl) fluorene] (PFN-OH) has also been investigated. They comprise the same polyfluorene backbone structures with, respectively, diethanolaminohexyl (PFN-OH) and diethanolaminohexoxyphenyl (PPFN-OH) substituents attached to the C9 carbon of the fluorene repeat unit. In comparison to reference devices with more reactive Ca/Al cathodes, utilizing these CPEs as interlayers allowed an Al cathode to be used for blue light emission PLEDs, yielding 51% and 92% enhancement of maximum luminous efficiency (LE) for PFN-OH and PPFN-OH, respectively. The PLEDs with PPFN-OH showed both higher maximum LE and maximum luminance (L) (LE = 2.53 cd/A at 6.2 V, L = 9917 cd/m2 at 8.3 V) than devices with PFN-OH (2.00 cd/A at 4.1 V, 3237 cd/m2 at 7.2 V). The PPFN-OH PLEDs also showed no significant roll-off in efficiency with increasing current density up to 400 mA/cm2, indicating excellent electron injection ability and stability for this interlayer. The insertion of alkoxy-phenyl groups at the C9-position in PPFN-OH is clearly advantageous. This simple modification significantly improves the CPE cathode interlayer performance. Parallel investigations of the electron extraction properties of PPFN-OH in inverted architecture PSCs with PCDTBT:PC70BM bulk heterojunction active layers demonstrated a power conversion efficiency enhancement of ∼19% (from 4.99% to 5.95%) for indium tin oxide cathode devices compared with reference devices using Ca/Al cathodes. These results confirm PPFN-OH to be a promising interlayer material for high performance solution processed organic optoelectronic devices. © 2014 Elsevier B.V. All rights reserved.