Reaction of [NH4]E[WS4] with CuX (X--C1 or I) and R4NX (R = Et or n-Bu) in the solid state gave two new bimetallic compounds with W:Cu compositions from 1:3 to 1:4. Compound (1), [(n-Bu)4N]3[WS4Cu3ClaBr], crystallizes in the hexagonal space group R3c with a = 17.051(5), c = 38.372(5)/~, V = 9661.8 ~3, Z = 6. The cluster anion of (1) comprises a cubane-like cluster core [WSaCu3Br] of C a symmetry with a C1 atom attached to each of the three Cu atoms and one terminal sulphido ligand attached to the W atom. Compound (2), [Et4N]4[WS4Cu416], crystallizes in the monoclinic space group C2/m with a=29.702(6), b=12.7887(5), c= 15.327(3)A, fl = 99.69(2) ~ V = 5738.1/~3, Z = 4. In the cluster anion of (2), four edges of the WS 4 core are coordinated by four Cu atoms, giving a WS4Cu 4 aggregate of approximate CEv symmetry.