Using scanning tunneling microscopy (STM), we characterize the atomic-scale details of ultrathin films of iron carbide (FexCy) on Au(111) synthesized as a potential model system for the active iron carbide phase in iron Fischer–Tropsch synthesis (FTS) catalysts. The experiments show that room-temperature exposure of Fe islands gas to C2H4 deposited on the clean Au(111) surface results in partly converted Fe/FexCy islands. Multistep flash-heating treatment of the partly converted Fe/FexCy islands at 523 and 773 K results in pure highly crystalline FexCy islands with in-plane nearest-neighbor distances of 0.315 ± 0.005 nm. On the basis of the atom-resolved STM data, we propose that C2H4 dissociates at Fe island edges, after which the carbon diffuses inward into the interstitial region between the Fe and the Au substrate to form an FexCy surface that may be a good starting point for the investigation of iron carbide surfaces present under FTS conditions.