Use water as solvent for the organic synthesis a great choice because it is economical, reduces waste and avoids potentially hazardous reagents versus the conventional solvents. This account presents the Cu(II)‐β‐CD as water soluble green catalyst for the one‐pot conversion benzyl halide to benzyl azide and 1,2,3‐trizoles at room temperature and very short reaction time (15‐70 min). Products are separated without any workup, simple by filtration, with >99 % selectivity and purity. As‐synthesized material was characterized by, HR‐TEM, XPS, FESEM, FT‐IR, TGA and XRD to understand its structural properties as well as attachment of copper by host‐guest interaction. This catalyst can also show effectiveness for the condensed ketone and aldehydes moiety, which produce biofuels intermediate. The recyclability of this catalytic system was tested up to five cycles and only a very slight loss of catalytic activity was detected.