Attempts to prepare the tricyclohexylphosphine or triphenylstibine analogues of the recently reported (triphenylphosphine) CuX2− anions were unsuccessful and instead resulted in the formation of a variety of polyhalocuprate anions. The structure of one of these, [CH3P(C6H5)3]2Cu2I4, has been determined; monoclinic, P21/c; a = 16.715(3), b = 10.787(2), c = 23.196(3) Å, β=98.59(1)°, Z=4; R=6.3%, Rw=3.1%. The 63Cu NQR spectra of twelve such polyhalocuprate anions were observed and the results compared with those of previously reported polyhalocuprates.