In order to further improve the energy conversion efficiency in reciprocating engines, detailed knowledge about the involved processes is required. One major loss source in internal combustion engines is heat loss through the cylinder walls. In order to increase the understanding of heat transfer processes and to validate and generate new heat transfer correlation models it is desirable, or even necessary, to have crank-angle resolved data on in-cylinder wall temperature.Laser-Induced Phosphorescence has proved to be a useful tool for surface thermometry also in such harsh environments as running engines. However, the ceramic structure of most phosphor coatings might introduce an error, due to its thermal insulation properties, when being exposed to rapidly changing temperatures. In this article the measurement technique is evaluated concerning the impact from the thickness of the phosphorescent layer on the measured temperature. Experiments with different layer thicknesses are performed both during motored and fired operation of a HCCI engine. The results reveal a need for caution when applying the technique for in-cylinder measurements.