A variety of trans-3,4-dihydroxy-1-selenolane {DHS(OH) 2 } derivatives of general formulae DHS(OH)OCH 2 C 10 H 7 , DHS(OCH 2 C 10 H 7 ) 2 (C 10 H 7 =naphthyl); DHS(OH)OCH 2 C 6 H 4 R-4, DHS(OCH 2 C 6 H 4 R-4) 2 (R=Me or OMe); DHS(OH)O(CO)CH 2 C 8 H 6 N, DHS{O(CO)CH 2 C 8 H 6 N} 2 (C 8 H 6 N=indolyl), and DHS(OH)O(CO)(CH 2 ) 4 O(CO)(HO)DHS have been synthesized. They were characterized by microanalyses, IR, NMR ( 1 H, 13 C{ 1 H}, and 77 Se{ 1 H}) spectroscopies and in some cases liquid chromatography–mass spectrometry (LC–MS). The naphthyl and indolyl substituted derivatives are fluorescent in solution. Molecular structure of DHS(OCH 2 C 10 H 7 ) 2 has been established by single crystal X-ray diffraction analysis.