Stability of functionalized surfaces is an often-neglected topic in phase-change heat transfer research. Here, we examine the chemical and morphological changes of textured surfaces on the molecular and atomic level after the critical heat flux incipience during saturated pool-boiling of water. SEM imaging, EDS, AES and XPS analyses are used to examine the surface changes. Copper samples were laser textured via ablation using a nanosecond fiber laser under air or argon atmosphere. Multiscale microcavities, which serve as preferential nucleation sites, were produced on the samples, which exhibited significantly enhanced heat transfer performance in pool-boiling tests. Repeated formation of a vapor film and accompanying temperatures of up to 320 degrees C during the tests resulted in changes of the surface chemistry and nanomorphology. It was determined that Cu (II) oxide and hydroxide transform into Cu (I) oxide and Cu metal as a result of repeated low-temperature annealing of the surface when a vapor film is formed during the transition towards film boiling. This additionally causes a wettability transition of the functionalized surfaces from hydrophilic towards hydrophobic. Both effects importantly influence the solid-liquid-vapor interface during phase-change heat transfer. Overall, surfaces functionalized via laser texturing exhibited significantly enhanced stability and boiling heat transfer performance.