The wall cooling induced by spray impingement is investigated using phosphor thermometry. Thin coatings of zinc oxide (ZnO) phosphor were applied with a transparent chemical binder onto a steel surface. Instantaneous spatially resolved temperatures were determined using the spectral intensity ratio method directly after the injection of UV-grade hexane onto the surface using a commercial gasoline injector. The investigations showed that 2D temperature measurements with high spatial and shot-to-shot precision of, respectively, 0.5 and 0.6 K can be achieved, allowing the accurate resolution of the cooling induced by the spray. The presence of a liquid film over the phosphor coating during measurements showed no noticeable influence on the measured temperatures. However, in some cases a change in the intensity ratio at the spray impingement area, in the form of a permanent "stain", could be observed after multiple injections. The formation of this stain was less likely with increasing annealing time of the coating as well as lower plate operating temperatures during the injection experiments. Finally, the experimental results indicate a noticeable influence of the thickness of the phosphor coating on the measured spray-induced wall cooling history. Hence, for quantitative analysis, a compromise between coating thickness and measurement accuracy needs to be considered for similar applications where the heat transfer rates are very high.