The total conductivity of the compositions containing Zr0.89Sc0.1Ce0.01O2 or Zr0.32Y0.08O2 powders and Cr2O3 was studied to evaluate a potential impact of the chromium deposition on the surface of electrolyte grains in the porous composite cathode. The compositions were fabricated in the corresponding ratios: (100-x) mol% Zr0.89Sc0.1Ce0.01O2 - x mol% CrO1.5 (10Sc1CeSZ-Cr) and (100-x) mol% Zr0.92Y0.08O2 - x mol% CrO1.5 (8YSZ-Cr) with x = 0.25, 0.5, 1, and 2. Porous ceramic Zr0.89Sc0.1Ce0.01O2 with 49% relative density exhibits higher conductivity than Zr0.92Y0.08O2. In general, a small addition of chromium decreases the conductivity of Zr0.89Sc0.1Ce0.01O2 and Zr0.92Y0.08O2, although the values of the conductivity change in a non-linear way, reaching minimum for 10Sc1CeSZ-Cr1 and 8YSZ-Cr0.25 compositions. This is accompanied by the decrease in the activation energy of the conductivity from 1.35 eV to 1.19 eV in the 10Sc1CeSZ-Cr series and from 1.28 eV to 1.19 eV in the 8YSZ-Cr series with the rise in the chromium content. Evolution of the conductivity values is associated with the interstitial incorporation of chromium into the fluorite structure as well as with its segregation on the surface of grains and grain boundaries. Chromium coexists in the multivalent states (Cr3+ and Cr6+) on the surface of grains. Considering a long-term operation of the SOFC system, one could suggest that Zr0.89Sc0.1Ce0.01O2 will show more promising transport characteristics in the presence of the chromium containing interconnects.