The magnetic state of electrodeposited iron on Au(1 1 1) substrates is investigated during the electrodeposition process by means of in situ alternating gradient force magnetometer (AGFM) and in situ perpendicular magneto-optic Kerr effect measurements (PMOKE). A perpendicular magnetic anisotropy (PMA) is observed for a thickness below 2 monolayers (ML). In situ STM observations of the initial stages of iron growth and ex situ EXAFS are used to correlate the structure of films to their magnetic properties.