A new method of oligo(nucleoside phosphorothioate)s (OligoS) synthesis, based on the oligonucleotide chain extention via DBU-catalyzed reaction of 5'-OH-nucleoside(-tide)with5'-DMT-nucleoside-3'-O-(2-thiono- 1.3.2-oxathiaphospholane)s (2) is elaborated. The process of oxathiaphospholane ring opening is shown to be chemo- and stereoselective. The use of separated diastereoisomers of 2 allows the synthesis of OligoS with a predetermined sense of chirality at each internucleotide phosphorothioate function.