Alkali fluorides, mostly LiF and CsF, are well-known to improve electron injection/extraction in organic light-emitting diodes (OLEDs) and organic solar cells (OSCs). They are also utilized, though to a lesser extent, for hole injection in OLEDs. Here we demonstrate a new role for such fluorides in enhancing OSCs’ hole extraction. We show that an ultrathin air-plasma-treated alkali fluoride layer between the indium tin oxide (ITO) anode and the active layer in copper phthalocyanine -based OSCs increases the short circuit current by up to for cells with LiF and for cells with NaF or CsF. The effects of the fluoride layer thickness and treatment duration were evaluated, as were OSCs with oxidized and plasma-treated Li and UV-ozone treated LiF. Measurements included current voltage, absorption, external quantum efficiency (EQE), atomic force microscopy, and x-ray photoelectron spectroscopy, which showed the presence of alkali atoms F and O at the treated ITO/fluoride surface. The EQE of optimized devices with LiF increased at wavelengths , exceeding the absorption increase. Overall, the results indicate that the improved performance is due largely to enhanced hole extraction, possibly related to improved energy-level alignment at the fluorinated ITO/CuPc interface, reduced OSC series resistance, and in the case of LiF, improved absorption.