Potassium (K) is an essential element, which is often supplied to horticultural crops via foliar spraying. Some studies have investigated the effect of different foliar-applied K compounds; however, most studies have focussed on crop quality and yield parameters, or were performed with isolated leaf cuticles. The aim of this study was to evaluate the rates of the foliar ion penetration and leaf surface deposition of 130 mM K sprays of compounds with markedly different point of deliquescence (POD) and efflorescence (POE) values, the rates having been previously estimated in climate chamber trials. Shoots of field-grown, commercial olive trees were sprayed with K-nitrate (KNO3), K-sulphate (K2SO4), K-chloride (KCl), K-phosphate (K3PO4), K-carbonate (K2CO3) and K-bicarbonate (KHCO3), and leaf samples were collected after 3 and 24 h. Cation and anion concentrations were determined in the leaf tissues, and in a preliminary leaf water wash for estimating surface-deposited ion concentrations. No significant leaf tissue K increments were recorded between the K sprays. Olive tissue anion concentrations showed different patterns, and a chloride (Cl−) increase was detected 3 h after the foliar KCl supply. On the other hand, the foliar K applications led to leaf nitrate changes regardless of the K source supplied. High amounts of K and accompanying ions were recovered in the washing liquid of the foliar K-supplied leaves. Some foliar K treatments increased the leaf surface concentration of sulphate and chloride, suggesting a potential effect on leaf cell anion extrusion. Hence, despite no evidence of foliar K uptake, an effect of leaf anion concentrations was observed, indicating that foliar nutrient sprays may influence leaf and leaf surface anion balance.