Reaction between [Fe2(μ-S2)(CO)6] and [Ca(thf)4(dpp-BIAN)] [dpp-BIAN = 1,2-bis-(2,6-diisopropyl-phenyl-imino)-acenaphthene and thf = tetra-hydro-furan] proceeds as a redox process via a two-electron reduction of [Fe2(μ-S2)(CO)6] and a two-electron oxidation of (dpp-BIAN)(2-), resulting in the formation of the title heterometallic trinuclear cluster, [CaFe2(μ3-S)2(C4H8O)4(CO)6], and neutral dpp-BIAN. In the cluster, the Ca(II) atom is connected to two S atoms of an Fe2S2 core [Ca-S = 2.7463 (8) and 2.7523 (8) Å]. No Fe-Ca bonds are formed [Fe⋯Ca = 3.6708 (6) and 3.5802 (6) Å]. There are five close C-H⋯O-C contacts in the crystal structure.