The iron-nickel films were deposited on the two metallic substrates (Cu, CuZn) from a mixture of iron and nickel salts and in the external magnetic field (EMF) presence. The films were electrodeposited in the fixed value of an electric current density and the time conditions. The EMF orientation and the electrochemical bath composition—molar ratio of Fe:Ni were changeable, parallel or perpendicular, and 1:1 or 1:2, respectively. Examined layers present variable surface morphologies and compositions depending on the substrates and the presence or absence of the EMF. Layers quality was analyzed using: scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction. Tribo-mechanical properties (roughness, wear tracks) were registered using a confocal laser scanning microscope. The observed results show that a variation in the surface morphology and the alloy composition is related to the electrolyte composition (Fe:Ni ratio) and the presence or absence of EMF. Higher Fe content in the electrolyte (Fe:Ni, 1:1) causes more significant anomalous deposition and an increase of tribo-mechanical parameters. The tribological parameters (Ssk, Sku, COF) depend on the electrolyte composition and substrate’s properties as a result of the film’s growth condition. The reduction in the thickness of the deposited layer (both electrolyte’s ratios) after applying an external magnetic field is the result of the increase of roughness parameters.