Catalytic alkene difunctionalization via Si−H and C−H activations represents an ideal atom‐ and step‐economic pathway for quick assembly of molecular complexity. We herein developed a visible‐light‐promoted metal‐free difunctionalization of alkenes using abundant CO2 and readily available Si−H and C(sp3)−H bonds as feedstocks. Through the merger of photoredox and hydrogen‐atom‐transfer catalysis, a variety of value‐added compounds, such as β‐silacarboxylic acids and acids bearing a γ‐heteroatom (e.g., N, O, S) could be directly accessed from simple alkenes in a redox‐neutral fashion. Photocarboxylation: Visible‐light‐promoted metal‐free difunctionalization of alkenes using CO2 and readily available Si−H and C(sp3)−H reagents has been realized by the merging of photoredox and hydrogen‐atom‐transfer catalysis. A variety of valuable compounds, such as β‐silacarboxylic acids and acids bearing a γ‐heteroatom (e.g., N, O, S) can be directly accessed from simple alkenes in a redox‐neutral fashion.