The reaction of Se(SiMe3)2 with mixtures of copper(I) chloride and indium(III) chloride in the presence of phosphine ligands PR3 (R = organic group) yielded the new clusters [Cu6In8Se13Cl4(PPh3)6(C4H8O)] 1, [Cu6In8Se13Cl4(PnPr2Ph)12] 2 and [Cu11In15Se16(SePh)24(PPh3)4] 3. The molecular structures of 1, 2 and 3 have been characterised by X-ray crystallography and compared with the chalcopyrite structure of bulk CuInSe2. UV-VIS Solid state absorption spectra have been measured for 1 and 3.