Adsorption, nucleation, and crystal growth of hafnium and titanium deposited from vapor in ultra-high vacuum onto thermally cleaned tungsten emitters have been studied by field electron emission microscopy methods. The Ti adsorption on W surface was typical of metals of low intersolubility. The local work function decreases monotonically under Ti adsorption and saturates. Local work function values at saturation were equal to 3.0 eV on the (016)W face, 3.5 eV on the (011)W and ( 111)W faces, 3.75 eV on the (001) W face, and 3.95 eV on the (112) W face. The Hf interaction with W was much stronger and much more anisotropic than the Ti-W interaction. The formation of an intermetallic compound between I-If and W caused strong decrease of the local work function on the {001} W faces, resulting in an unusually high electron emission from these areas.