Heterodialkylation of [Pt2(mu-S)2(dppp)2] (dppp = Ph2P(CH2)3PPh2) was achieved under high pressure (10 kbar). This enabled the synthesis of rare diplatinum complexes with structurally diverse thiolate bridges, such as [Pt2(mu-SC5H10CO2CH2CH3)(mu-SC3H7)-(dppp)2](PF6)2, which was crystallographically identified. Complete homodialkylation was also achieved under similar conditions (6 kbar at room temperature), thus permitting the isolation of [Pt2(mu-SC2H4CO2CH2CH3)2(dppp)2]-(PF6)2. The isolation of these complexes extends the applications of high-pressure chemistry to thiolato homo- and heterobridged complexes that are otherwise not accessible.