Currently, most catalysts used for photoconverting carbon dioxide (CO2) typically produce C1 products. Achieving multicarbon (C2+) products, which are highly desirable due to their greater energy density and economic potential, still remains a significant challenge. This difficulty is primarily due to the kinetic hurdles associated with the C-C coupling step in the process. Given this, devising diverse strategies to accelerate C-C coupling for generating multicarbon products is requisite. Herein, we first give a classification of catalysts involved in the photoconversion of CO2 to C2+ fuels. We summarize metallic oxides, metallic sulfides, MXenes, and metal-organic frameworks as catalysts for CO2 photoreduction to C2+ products, attributing their efficacy to the inherent dual active sites facilitating C-C coupling. In addition, we survey covalent organic frameworks, carbon nitrides, metal phosphides, and graphene as cocatalysts for CO2 photoreduction to C2+ products, owing to the incorporated dual active sites that induce C-C coupling. In the end, we provide a brief conclusion and an outlook on designing new photocatalysts, understanding the catalytic mechanisms, and considering the practical application requirements for photoconverting CO2 into multicarbon products.