Resiniferatoxin (1) is a complex daphnane diterpenoid with a highly oxygenated 5/7/6-membered ABC-ring system. Here we report a new synthetic route to 1 that requires 27 steps from a starting d-ribose derivative. The carbon spacer and A-ring are sequentially attached to the C-ring by radical allylation and Stille coupling reactions, respectively. An Ir(III)-catalyzed photoinduced decarboxylative radical reaction then forged the sterically hindered bond between the tetra- and trisubstituted carbons to cyclize the central seven-membered B-ring.