A study of hybrid light-emitting diodes (HyLEDs) fabricated with and without solution-processible Cs2CO3 and Ba(OH)2 inorganic interlayers is presented. The interlayers are deposited between a zinc oxide electron-injection layer and a fluorescent emissive polymer poly(9-dioctyl fluorine–alt-benzothiadiazole) (F8BT) layer, with a thermally evaporated MoO3/Au layer used as top anode contact. In comparison to Cs2CO3, the Ba(OH)2 interlayer shows improved charge carrier balance in bipolar devices and reduced exciton quenching in photoluminance studies at the ZnO/Ba(OH)2/F8BT interface compared to the Cs2CO3 interlayer. A luminance efficiency of ≈28 cd A−1 (external quantum efficiency (EQE) ≈ 9%) is achieved for ≈1.2 μm thick single F8BT layer based HyLEDs. Enhanced out-coupling with the aid of a hemispherical lens allows further efficiency improvement by a factor of 1.7, increasing the luminance efficiency to ≈47cd A−1, corresponding to an EQE of 15%. The photovoltaic response of these structures is also studied to gain an insight into the effects of interfacial properties on the photoinduced charge generation and back-recombination, which reveal that Ba(OH)2 acts as better hole blocking layer than the Cs2CO3 interlayer.