Commercial use of lead halide perovskites requires improved thermal stability and therefore a better understanding of their degradation mechanisms. The thermal degradation of three clean perovskite single crystal surfaces (MAPbI3, MAPbBr3, FAPbBr3) was investigated using synchrotron-based photoelectron spectroscopy. Central findings are that the halide has a large impact on thermal stability and that the degradation of formamidnium results in the formation of a new organic species at the FAPbBr3 crystal surface.