Oxidative dehydrogenation of ethane with CO2 (ODEC) is an attractive reaction for reduction of carbon footprints and ethene production. In this work, we present photothermal catalysis on confined bimetal catalysts for ODEC. Carbon nanotubes confined non-noble bimetal alloy (i.e., CoNi@CNTs and FeNi@CNTs) catalysts were prepared and FeNi@CNTs showed effective performance in photothermal catalytic ODEC to ethene. Experiments and simulations reveal that UV and visible lights (420 – 490 nm) are responsible for ODEC and non-oxidative dehydrogenation of ethane, respectively, to ethene. Additionally, ODEC to ethene is preferred to C-C cracking to methane on FeNi@CNTs in light (> 490 nm)-induced thermocatalysis. The photothermal effect turns more significant when introduced into thermocatalytic ODEC (500 °C), with ethene generation at one order of magnitude. This work advances new mechanism of photo-mediated catalysis and sheds light on utilization of full-spectrum solar energy and non-noble metallic catalysts for ethene production and CO2 recycling at moderate conditions.