A photocatalytic domain of doubly decarboxylative Csp2−Csp2 cross coupling reaction is disclosed. Merging iridium and palladium photocatalysis manifested carbon‐carbon bonds in a tandem dual‐radical pathway. Present catalytic platform efficiently cross‐coupled α, β‐unsaturated acids and α‐keto acids to afford a variety of α, β‐unsaturated ketones with excellent (E)‐selectivity and functional group tolerance. Mechanistically, photocatalyst implicated through reductive quenching cycle whereas cross coupling proceeded over one electron oxidative pallado‐cycle. [ABSTRACT FROM AUTHOR]