An expeditious route to planar chiral sulfur-based scaffolds has been achieved in two operational steps from cheap and commercial [2.2]paracyclophane hydrocarbon. The sulfur atom was introduced in a specific benzylic position of the [2.2]paracyclophane according to a reductive sulfanylation reaction, which proceeds under two complementary reaction conditions with either the BF3·OEt2/Et3SiH or TFA/BH3·THF combinations. The study was completed by the development of a highly efficient resolution approach by HPLC.