Photothermal catalysis, recognized as an efficient approach for solar-to-chemical conversion, enhances catalytic reactions more effectively under mild conditions. However, there are problems concerning low atomic utilization efficiency, poor intrinsic catalytic activity, and selectivity. Therefore, it is highly imperative that the development of photothermal catalysts with excellent activity, selectivity, and stability remains the key challenge in this field. Based on this, the rational design of highly efficient photothermal catalysts should satisfy three criteria: (1) excellent sunlight absorption ability, (2) effective thermal management to prevent heat dissipation, (3) great intrinsic reactivity for efficient catalytic performance, and (4) a special photochemistry effect. Confronted with this key challenge, our work primarily focuses on the construction of efficient photothermal catalysts. First, we have developed an ideal type of photothermal material (MXene) to enhance the photothermal catalytic performance. Second, we have designed a catalyst architecture that enables “supra-photothermal” CO₂ catalysis to reduce heat loss. Third, we developed efficient sunlight-driven MXene-supported metal cluster catalysts with sufficient metal dispersity and stability. Our work will provide guidance for the rational design of efficient photothermal CO₂ catalysts. Fourth, we report the discovery of anisotropic localized surface plasmon resonance (LSPR) in Ti3C2Tx MXene as well as site-selective photocatalysis enabled by the photophysical anisotropy. Both experimental and theoretical studies provide direct evidence of the occurrence of transverse and longitudinal dipolar plasmon resonance modes in the two-dimensional MXene nanoflakes.