The effect of transition metal substitution on thermal and electrical properties of Ca-doped yttrium chromite was investigated in relation to use as a ceramic interconnect in high temperature solid oxide fuel cells (SOFCs). 10 at.% Co, 4 at.% Ni, and 1 at.% Cu substitution on B-site of 20 at.% Ca-doped yttrium chromite led to a close match of thermal expansion coefficient (TEC) with that of 8 mol% yttria-stabilized zirconia (YSZ), and a single phase Y0.8Ca0.20Cr0.85Co0.1Ni0.04Cu0.01O3 remained stable between 25 and 1100 degrees C over a wide oxygen partial pressure range. Doping with Cu significantly facilitated densification of yttrium chromite. Ni dopant improved both electrical conductivity and dimensional stability in reducing environments, likely through diminishing the oxygen vacancy formation. Substitution with Co substantially enhanced electrical conductivity in oxidizing atmosphere, which was attributed to an increase in charge carrier density and hopping mobility. Electrical conductivity of Y0.8Ca0.20Cr0.85Co0.1Ni0.04Cu0.01O3 at 900 degrees C is 57 S cm(-1) in air and 11 S cm(-1) in fuel (pO(2) = 5 x 10(-17) atm) environments. Chemical compatibility of doped yttrium chromite with other cell components was verified at the processing temperatures. Based on the chemical and dimensional stability, sinterability, and thermal and electrical properties, Y0.8Ca0.20Cr0.85Co0.1Ni0.04Cu0.01O3 is suggested as a promising SOFC ceramic interconnect to potentially overcome technical limitations of conventional acceptor-doped lanthanum chromites. (C) 2011 Elsevier B.V. All rights reserved.