Increased cooling requirements of many compact systems involving high heat fluxes demand the development of high-performance cooling techniques including immersion cooling utilizing pool boiling. This study presents the functionalization of copper surfaces to create interfaces for enhanced pool boiling heat transfer. Three types of surface structures including a crosshatch pattern, shallow channels and deep channels were developed using nanosecond laser texturing to modify the surface micro- and nanomorphology. Each type of surface structure was tested in the as-prepared superhydrophilic state and superhydrophobic state following hydrophobization, achieved through the application of a nanoscale self-assembled monolayer of a fluorinated silane. Boiling performance evaluation was conducted through three consecutive runs under saturated conditions at atmospheric pressure utilizing water as the coolant. All functionalized surfaces exhibited enhanced boiling heat transfer performance in comparison with an untreated reference. The highest critical heat flux of 1697 kW m−2 was achieved on the hydrophobized surface with shallow channels. The highest heat transfer coefficient of 291.4 kW m−2 K−1 was recorded on the hydrophobized surface with deep channels at CHF incipience, which represents a 775% enhancement over the highest values recorded on the untreated reference. Surface microstructure was identified as the key reason for enhanced heat transfer parameters. Despite large differences in surface wettability, hydrophobized surfaces exhibited comparable (or even higher) CHF values in comparison with their hydrophilic counterparts, which are traditionally considered as more favorable for achieving high CHF values. A significant reduction in bubble departure diameter was observed on the hydrophobized surface with deep channels and is attributed to effective vapor entrapment, which is pointed out as a major contributing reason behind the observed extreme boiling heat transfer performance.