Recent studies have indicated that at slightly superheated surface temperatures, droplet evaporation on a nanoporous superhydrophilic surface exhibits onset of nucleation and nucleate boiling effects similar to pool boiling processes. This paper discusses water droplet evaporation experiments and pool boiling experiments conducted on nanostructured surfaces of a 45° downward facing pyramid copper and aluminum substrate. The nanostructured surfaces were used to conduct both droplet evaporation experiments and pool boiling experiments and thus allow direct comparison of the underlying heat transfer performance and mechanisms for these two different processes. The four surfaces tested were the following: bare copper surface, nanostructured surface on copper, bare aluminum surface, and nanostructured surface on aluminum. Mean heat flux values at varying superheats were obtained through temperature and time measurements. To better understand the heat performance of each surface, the wetting and wicking characteristics of each surface were also tested. Experimental results indicate that many of the mechanisms associated with pool boiling may also play a role in droplet vaporization, and their presence can produce levels of heat transfer performance comparable to, or even higher than, that observed in pool boiling at a comparable wall superheat. The results demonstrate that the nanostructured surface affects onset of nucleate boiling and maximum heat flux in both droplet vaporization and nucleate boiling on these surfaces. The implications of these results for strategies to enhance spray cooling and pool boiling are also discussed.