A 1D Cu(I)-coordination polymer [(CuL1)(CuBr₂), 1] carrying external copper bromide moieties was synthesized. The outer-hanging [CuBr₂]⁻ moiety is attached to the 1D Cu(I)-CP backbone via a Cu⋯Cu bonding interaction, which makes it look like a coordination polymer supported CuBr₂ species. 1 exhibits excellent multifunctional catalytic activity for phenol acetylation, A³-coupling (aldehyde–alkyne–amine) and styrene oxide methanolysis reactions. Its heterogeneous catalytic nature was confirmed by solution leaching experiment and it can be reused without significant loss of its catalytic activity and selectivity for the above reactions.