We are inspired by the intense research in developing 2D materials, single-atom catalysts (SACs) and sustainable photo-biorefinery approach for thermo-photocatalytic (TPC) reactions because its high activity and stability maximize the conversion of CO2 utilization/ valorisation of organic waste into useful chemicals. In this context, we aim to accelerate the rational designing of plasmon-induced 2D supported atomic sites catalysts, including SACs and single-atom alloy catalysts for TPC applications. Ideally, the rational design and optimization of these hybrid materials should progress based on prior detailed knowledge of the basic intrinsic properties of each material involved and their atomic-level molecular interactions. To date, limits on the choice of 2D-supported SACs have been studied. However, very few reports are on a hybrid of plasmon-induced 2D-supported SACs catalysts for TPC reactions. Intriguing, we thus intend to use these plasmonic-2D-SACs catalysts to significantly accelerate the discovery of realistic TPC simultaneous conversions of CO2 into affordable hydrocarbons and furanic compounds obtained from lignocellulosic organic waste. The oxidation of 5-hydroxymethyl furfural (HMF) and furfural (FUR) produces strong market value compounds in the polymer industry. However, the selective oxidative dehydrogenation of HMF results in 2, 5, diformylfuran (DFF), and hydrogen (H2). The generated H2 can be an attractive feedstock for widely studied hydrogenation reactions. However, a recent oxygen free methodology needs to be incorporated considering the several challenges of this oxidation reaction (HMF to DFF). Here, we will target to exploit the advanced strategy in combination with plasmonic-2D-SACs for TPC selective dehydrogenation of HMF. Thus, the conversion activity of CO2 and HMF & FUR is not only induced due to light and heat energy; however, it can also be enhanced by providing concomitant hydrogen obtained from oxidative dehydrogenation of HMF and FUR.