The results of study of metal-alloyed palladium-barium emitters' of modem very high frequency high-powered electronic vacuum tubes by scanning electron microscopy (SEM) and scanning tunneling microscopy/spectroscopy (STM/STS) are presented. Since the Pd/Ba foil surface is fairly smooth and is not oxidized in air STM/STS investigations are carried out in air in normal laboratory environment. SEM and STM images show that the emitter surface has a complex porous structure. The cathode surface study by STS in tunneling gap modulation mode allowed to take a map of phase distribution with various work function values and high lateral resolution. Obtained images demonstrate the presence of three phases on the Pd/Ba emitter surface, viz. barium-oxygen compounds, intermetallic, and palladium. As it is seen from presented STS image the phase with a low work function value (barium oxides) is concentrated along boundaries of the substance inclusions with work function corresponding to the intemetallic compound Pd5Ba. This supports the model of low work function areas obtained via Ba segregation from the intermetallic compound and oxidation. The presented methods may be used in the Pd/Ba cathode manufacturing process for increasing the yield of electronic devices in microwave tube production and optimize the emitters' characteristics. (C) 2003 Elsevier Science B.V. All rights reserved.