A concise and divergent synthesis of the polychlorinated marine steroids clionastatin A and B from inexpensive testosterone has been achieved through a unique two-stage chlorination-oxidation strategy. Key features of the two-stage synthesis include (1) conformationally controlled, highly stereoselective dichlorination at C1 and C2 and C4-OH-directed C19 oxygenation followed by a challenging neopentyl chlorination to install three chlorine atoms; (2) desaturation through one-pot photochemical dibromination-reductive debromination and anti-Markovnikov olefin oxidation by photoredox-metal dual catalysis to enhance the oxidation level of the backbone; and (3) Wharton transposition to furnish the D-ring enone. This synthesis proved that the introduction of the C19 chloride in the early stage of the synthesis secured the stability of the backbone against susceptibility to aromatization during the oxidation stage.