X‐ray photoelectron forward scattering and CO‐titration measurements show that Fe agglomerates on Cu(111). Deposition of 6 monolayers of Fe at 300 K covers only ∼90% of the substrate. However, deposition of 3 monolayers of Fe at 80 K covers ∼95% of the substrate. The changing film morphology is reflected in the epitaxial phase of the Fe film. Fe deposited on Cu(111) at a substrate temperature of 80 K grows body‐centered‐cubic (bcc), but Fe deposited at a substrate temperature of 300 K initially grows face‐centered‐cubic and relaxes to bcc with increasing thickness. The changing epitaxial crystalline phase is discussed in terms of the intrafilm interaction strength relative to the film–substrate bond strength.