We investigated the electronic properties of composite-type hybrid transparent conductive electrodes (h-TCEs) based on Ag nanowire networks (AgNWs) and indium tin oxide (ITO). These h-TCEs were developed to replace ITO, and their mechanical flexibility is superior to that of ITO. However, the characteristics of charge carriers and the mechanism of charge-carrier transport through the interface between the h-TCE and an organic material are not well understood when the h-TCE is used as the anode in a flexible organic light-emitting diode (f-OLED). AgNWs were spin coated onto polymer substrates, and ITO was sputtered atop the AgNWs. The electronic energy structures of h-TCEs were investigated by ultraviolet photoelectron spectroscopy. f-OLEDs were fabricated on both h-TCEs and ITO for comparison. The chemical bond formation at the interface between the h-TCE and the organic layer in f-OLEDs was investigated by X-ray photoelectron spectroscopy. The performances of f-OLEDs were compared based on the analysis results.