Perovskite　oxide　(La,Sr)TiO3+δ　(LSTO)　cathode　has　demonstrated　promising　performance　for　direct　CO2　electrolysis　due　to　its　unique　redox-stable　properties.　However,　insufficient　electro-catalytic　activity　of　titanate　remains　a　major　drawback　that　limits　electrode　performance.　In　this　paper,　catalytically　active　scandium　is　doped　to　LSTO　to　enhance　cathode　performances.　The　structure,　electronic　conductivity　and　ionic　conductivity　of　La0.2Sr0.8Ti1−xScxO3+δ　(LSTSxO)　(x = 0,　0.05　and　0.1)　are　investigated　and　further　correlated　with　electrode　performances.　XRD,　TEM,　TGA　and　XPS　indicate　the　successful　partial　replacement　of　Ti　by　Sc　in　the　B　site　of　titanate.　The　improved　electrode　performances　are　strongly　dependent　on　scandium　doping　contents.　Promising　direct　CO2　electrolysis　performance　is　demonstrated　with　near　100%　current　efficiency　based　on　La0.2Sr0.8Ti0.9Sc0.1O3+δ　at　1.7 V　and　800 °C.　©　2017　Hydrogen　Energy　Publications　LLC