Abstract: Dry reforming of methane (DRM) is a promising technology for converting greenhouse gases (CH4 and CO2) into syngas, but it is typically hindered by high energy barriers and rapid catalyst deactivation due to severe coking. This work presents a comprehensive study on designing advanced Ni-based catalysts to overcome these challenges through active site engineering and photothermal catalysis. First, we reveal the non-thermal effects of light on Ni/Ga2O3, where light irradiation reverses the electron transfer direction and generates hot electrons, effectively tuning the H2/CO ratio near unity by suppressing the reverse water-gas shift reaction. Second, moving to single-atom catalysis on NiSA/CeO2, we demonstrate that light irradiation reinforces the formation of the key anti-coking intermediate (CH3O*), achieving exceptional stability for over 230 hours at a low temperature of 472 °C. Third, we explore heteroatom doping strategies to stabilize active sites. Praseodymium-modified CeO2 (Ni/Pr-CeO2) is found to facilitate direct carbonate cleavage under light, significantly boosting CO yield, while Molybdenum-stabilized Nickel-oxo sites (NiMo/MgO) enable a "hydroxyl-mediated" pathway involving CH2OH intermediates, further lowering the activation temperature to 465 °C. Finally, we scale up these concepts to a concentrated-solar catalytic system using Ni-O4 coordinated sites on CeO2(100), achieving ultrahigh conversion (>93%) and light-to-chemical energy conversion efficiency (25.9%) with over 800 hours of durability. These findings collectively provide critical mechanistic insights into C-H/C-O bond activation and offer a multidimensional roadmap for developing sustainable, solar-driven C1 chemistry technologies.