Five-coordinated trithiotungsten complexes (PPh4)[(dMSP)W(S)(3)] (1a) and (PPh4)[(dPSP)W(S)(3)] (1b) (R2PCH2CH2S- R = Me (dmsp(-)), Ph (dpsp(-))) were synthesized by addition of Hdmsp and Hdpsp to a THF solution of (PPh4)[(EtS)W(S)(3)]. Treatment of la with CuBr in the presence of PPh3 in CH3CN afforded a WCU2 cluster (dMSP)WS3CU2(PPh3)(2)Br (2). The reaction of la with 1 equiv of FeCl2 went smoothly to generate a 1:1 adduct (PPh4)[(dMSP)WS3(FeCl2)] (3), while 3 did not react further with excess FeCl2. On the other hand, 3 was found to react with [Fe(CH3CN)(6)](CIO4)(2), giving rise to an unusual tetranuclear cluster, [(dMSP)WS3](2)Fe2Cl (4), while the reaction of 1a with 2 equiv of [Fe(CH3CN)(6)](CIO4)(2) led to a cyclic octanuclear cluster[(dmsp)WS3Fe](4) (5). Although the oxidation states of W(VI), Cu(I), and Fe(II) are retained in 2 and 3, reduction of the metal ions occurs in the formation of 4 and 5. All the complexes reported in this paper were structurally characterized by X-ray analysis. It is anticipated that the new type of trithiotungsten complexes, 1a and 1b, will serve as potential synthons for various heterometallic sulfide clusters.