Transitioning from fossil dependence toward sustainable fuel architecture requires green chemical pathways capable of generating drop-in hydrocarbon biofuels directly from biomass. Herein, we present a metal-free, visible-light-driven photoredox strategy employing a sodium iodide and triphenylphosphine (NaI/PPh 3 ) catalytic system for the selective hydrodecarboxylation of long-chain fatty acid-derived redox-active esters. Operating at room temperature (25 °C) and atmospheric pressure (1 atm) under blue LED irradiation (λ≈ 450 nm), and utilizing Hantzsch ester as a hydrogen donor, this protocol cleanly converts saturated fatty acid derivatives into linear n-alkanes C 9 –C 17 with yields up to 88%. The process eliminates the need for molecular hydrogen, noble-metal complexes, organic dye sensitizers, or high-temperature processing. The methodology was further adapted into a streamlined one-pot protocol directly from free fatty acids and successfully validated on mixed fatty acid feeds, yielding hydrocarbon distributions matched to sustainable aviation fuel (SAF) and green diesel specifications. Mechanistic insights confirm the key role of an electron donor–acceptor (EDA) complex in driving radical cleavage. Overall, this work establishes a benign, highly selective, and low-cost photochemical platform for converting renewable lipid derivatives into drop-in fuels.