The photochemistry of 6,6'-dibromo-BINOL (BINOL = 2,2'-dihydroxy-1,1'-binaphthyl) under mild basic conditions and its methyl and triisopropylsilyl ethers has been investigated in neat and aqueous acetonitrile through product distribution analysis and laser flash photolysis. Arylation and alkylation have been successfully achieved in the presence of allyltrimethylsilane, ethyl vinyl ether, pyrrole, pyridine, thiophene, benzene, and indole. Such a photoreactivity offers a metal and protecting group free synthetic protocol toward mono- and disubstituted 6-aryl/alkyl BINOLs, since the BINOL chirality is preserved in the photoactivation process.