Display omitted •Transition-metal-free approach towards Glaser- and Cadiot-Chodkiewicz-type Coupling.•Regioselective synthesis of 1,3-diynes and 1,3-enynes.•Chemical transformations were possible in aqueous medium.•Organocatalyzed chemical transformations.•Broad substrate scope with high yields of the products. Efficient and transition-metal-free transformations towards the synthesis of 1,3-diynes have been described from their corresponding terminal acetylenes or 1,1-dibromo-1-alkenes. The efficiency of molecular iodine as catalyst in aqueous medium, driven the transformation to afford 1,3-diynes in moderate to good yields. The developed reaction conditions revealed appreciable functional group tolerance in aqueous medium. Further, the scope of the transition-metal-free approach for the synthesis of 1,3-enynes has been investigated using terminal alkynes as easy available precursors.