This paper describes a new efficient synthesis of 2, 2′-spirobi-(1, 3-benzoxathiole)(1), 2, 2′-spirobi-(1, 3-benzodithiole)(2) and 2, 2′-spirobi-(1, 3-benzodioxole)(3). Compound 3 has been functionalized by means of metallation reaction followed by electrophilic quenching to give carboxylic acids, aldehydes and alcohols. Furthermore compound 3 was subjected to homo-coupling and its dimeric structure was determined by XRD analysis.