A-site substituted cerium metavanadates, Ce(1-x)Ca(x)VO(3), were synthesised by solid-state reactions from single-phase powders of the corresponding orthovanadates. All metavanadate samples were found to exhibit either an orthorhombic and/or monoclinic phase of space group Pnma (62) with a = 5.5067 (4), b = 7.7904 (5) and c = 5.4814(7) angstrom for Ce(0.8)Ca(0.2)VO(3). X-Ray diffraction patterns and thermal analyses have shown that the reduction of Ca-doped CeVO(3) from the equivalent orthovanadate is redox phase reversible without formation of parasitic phases at x = 0.2, 0.3. Conductivity measurements were performed in air and in dry 5 H(2)-Ar with conductivity of Ce(1-x)Ca(x)VO(3) ranging from 1.5 to 13 S cm(-1) at 700 degrees C in a reducing atmosphere. Sample Ce(0.7)Ca(0.3)VO(3) exhibits the highest conductivity in a reducing atmosphere in all the measured samples which could be a potential anode or as a part of composite anode for SOFCs. The conductivity of Ce(0.7)Ca(0.3)VO(3) is higher than that for Ce(0.85)Sr(0.15)VO(3) which could be related to the higher doping level.