An efficient and cost‐effective Cu (I) mediated protocol for the C(sp2)–C(sp) cross‐coupling of 3‐chalcone‐2‐chloroquinoline with terminal alkynes has been disclosed by optimizing a wide range of catalysts, ligands, base, and solvents. This approach conveniently assembles various alkynylated hybrids with excellent to moderate yields. Appropriate functional group tolerance and significant mechanistic pathway with mild reaction conditions well‐justified this synthetic transformation more sustainable towards the greener exploration.