An efficient procedure for the one-pot synthesis of propargylamines is A(3) coupling in which an alkyne, an aldehyde, and an amine are coupled together. Here, we report that polystyrene supported Cu(I) catalyst is excellent for A(3) coupling in water without using any additives or hazardous organic solvents. The polystyrene supported Cu(I) catalyst was synthesized and its catalytic activity was also evaluated in the synthesis of propargylamines in oxidative A(3)-coupling reaction with benzyl alcohols instead of their aldehydes in water. This protocol offers several advantages such as high yields of the desired product, reaction in aqueous medium and recyclability of the catalyst. It gives well to excellent yields for a variety of substrates. As it acts as heterogeneous catalyst, it can be easily separated from the reaction mixture and reused without appreciable loss of activity. Polymer supported copper catalyst, Cu-PS-ala, acts as a heterogeneous catalyst for the one pot synthesis of propargylamines via A(3) coupling reaction in water using aldehydes or alcohols, amines and alkynes.