Our direct C-H functionalisation strategy enables selective modification at the most electrondeficient position on a broad range of electron-poor aromatics in an 'Anti-Friedel-Crafts' alkylation manner (Fig. ). Our photocatalyst-free method utilises inexpensive and commercially available catalysts, without requiring harsh acidic or pyrophoric reagents. The mild reaction conditions tolerate a wide range of functional groups, including halide handles to facilitate further down-stream functionalisation. Mechanistic investigations reveal that the EDA activation between DABCO (1,4-diazabicyclo[2.2.2]octane) and a redox active phthalimide ester (RAE) serves as the trigger for a chain-like, autocatalytic radical reaction. This high regioselectivity and functional group tolerance was exploited for the late-stage modification of pharmaceuticals and agrochemicals (Fig. ). The observed 'Anti-Friedel-Crafts' regioselectivity can be readily tuned with aromatic substituents, as predicted by density functional theory (DFT) calculations and machine learning models.