Experimental investigation of pool boiling is conducted in stationary conditions over very smooth bronze surfaces covered by a very thin layer of gold presenting various surface treatments to isolate the role of wettability. We show that even with surfaces presenting mean roughness amplitudes below 10 nm the role of surface topography is of importance. The study shows also that wettability alone can trigger the boiling and that the boiling position on the surface can be controlled by chemical grafting using for instance alkanethiol. Moreover, boiling curves, that is, heat flux versus the surface superheat (which is the difference between the solid surface temperature and the liquid saturation temperature), are recorded and enabled to quantify, for this case, the significant reduction of the superheat at the onset of incipient boiling due to wettability.