The one‐step syntheses, X‐ray structures, and spectroscopic characterization of synthetic iron clusters, bearing either inorganic sulfides or thiolate with interstitial carbide motifs, are reported. Treatment of iron carbide carbonyl clusters Fen(μn‐C)(CO)mx (n=5,6; m=15,16; x=0,−2) with electrophilic sulfur sources (S2Cl2, S8) results in the formation of several μ4‐S dimers of clusters, and moreover, iron‐sulfide‐(sulfocarbide) clusters. The core sulfocarbide unit {C−S}4− serves as a structural model for a proposed intermediate in the radical S‐adenosyl‐L‐methionine biogenesis of the M‐cluster. Furthermore, the electrophilic sulfur strategy has been extended to provide the first ever thiolato‐iron‐carbide complex: an analogous reaction with toluylsulfenyl chloride affords the cluster Fe5(μ5‐C)(SC7H7)(CO)13−. The strategy described herein provides a breakthrough towards developing syntheses of biomimetic iron‐sulfur‐carbide clusters like FeMoco. At first glance, CO‐supported iron‐carbide clusters are an appealing synthetic starting point for modeling the carbide‐containing FeMoco cluster. However, these compounds have historically been uncontrollable towards traditional CO→S substitution methods. Demonstrated here is an approach utilizing unconventional electrophilic sulfur reagents to achieve carbide‐containing multi‐sulfide multi‐iron clusters.