Methane dry reforming with CO2 is greatly affected by the presence of various form of surface carbon (carbides, graphite, carbon nanotubes (CNT), etc). To characterize them two methods have been chosen: (i) temperature programmed oxidation (TPO) and (ii) transmission electron microscopy (TEM). CeZrNi, CeZrNiCo, CeZrNiRh and 5%Ni/CeZr catalysts were prepared by sol-gel and impregnated method, respectively. These catalysts are efficient in dry reforming of methane reaction. The surface carbon obtained during the reforming process was generally characterized by Tmax in TPO. On sol/gel CeZrNi(s/g) and impregnated Ni/CeZr(imp.) catalysts the Tmax appeared at 400oC and at 600°C, respectively, which shows different carbon structures. Simultaneously, TEM image pointed out the extensive CNT formation on the impregnated Ni catalyst along with an increase in Ni particle size while for the sol/gel sample the Ni particles are stabilized in the form of Ni nanoparticles. On bimetallic CeZrNiCo(s/g) and CeZrNiRh(s/g) catalysts two kinds of surface carbon species coexist. These characterized by Tmax at 360°C was slowly transformed to those at higher temperature peak (600°C). The amount of carbon is considerably higher on the Co containing sample than for one with Rh. We can speculate that on CeZrNiCo sample the carbidic (CoCx or NiCx) species are predominantly formed and after the changing of catalyst structure the CNT and graphitic species become prevailing.