In summary, we have developed a modular synthetic route to unsymmetric 1,4-diketones through the combination of benzoyl fluorides, styrenes and α-keto acids catalysed by a dual catalytic NHC/photoredox system using the recently developed MR-TADF organophotocatalyst DiKTa. During the development of this system Zhang and co-workers published a similar methodology requiring an iridium-containing photocatalyst. Certain substrates performed better under their conditions, although most 1,4-diones were obtained in comparable yields using the metal-free conditions described herein. Further work will probe alternative strategies to utilise the reactivity of DiKTa in other photocatalytic transformations.