The composition of the surface of pyrographite modified with VOCl3 vapor and the influence of the conditions of synthesis on it were investigated with the use of x-ray photoelectron spectroscopy. A significant effect was established for the nature of the carrier gas used (air, nitrogen, helium) on both the concentration of elements in the surface layer and the shape of the V 2p3/2, C 1s, and O 1s bands observed in the photoelectron spectrum. On the basis of comparative analysis of spectra of modified pyrographite and bulk oxygen compounds of vanadium it was proposed that structures close in nature to hydrated vanadium(V) oxide are formed on the surface of pyrographite. The concentration and degree of polycondensation of the surface structures are controlled by the content of oxygen in the carrier gas.