The first example of asymmetric alkene-alkene reductive coupling is demonstrated via visible-light-fueled photoredox/cobalt dual catalysis. The desymmetrization reaction provided products (>20 examples) with up to five chiral centers in single-step operation in up to 95% yields with very high relative (>99 : 1 dr) and absolute stereochemistry (up to 98 : 2 er) control. The preliminary mechanistic investigations suggested that the critical mechanistic steps involved light-mediated controlled low-valent cobalt complex generation, oxidative ene-ene cyclization, and protonation.