A new salt, [BrBzTPP][CuBr3](1) ([BrBzTPP]+ = 1-(4'-bromobenzyl)triphenylphosphinium), was simply synthesized by the direct reaction of CuBr2 and [BrBzTPP]Br in methanol and characterized by elemental analyses, IR, MS spectra and single crystal X-ray diffraction. The crystal is monoclinic space group, P21/c, a = 9.279(1) Å, b = 16.129(2) Å, c = 17.545(3) Å, β = 101.54(1)°, V = 2572.7(7) Å3, Z = 4. The Cu(II) ions of the title complex form a dimer with Cu···Cu distance of 3.597 Å through Cu··Br coordination bond, while the [BrBzTPP]+ form a 1D chain by weak C-H···π hydrogen bond with a H···π distance of 3.098 Å. [ABSTRACT FROM AUTHOR]