<p>A copper(I) complex [CuCl{<i>k</i>¹(P)-<b>1a</b>}{k²(P,N)-<b>1a</b>}] (<b>1a</b> = 2,5-bis(2-pyridyl)-1-phenylphosphole) with pseudo tetrahedral geometry was synthesized. In solution, <b>1a</b> displays a hemilabile behaviour leading to a dynamic equilibrium between four and three-coordinate specie. Its catalytic potential was tested in synthesis of propargylamines and 1,2,3-triazoles via three-component reactions. <a>Experimental results discussed on base to DFT calculations. </a></p>