Fe/Al multilayers with different composition were prepared by conventional, direct-pulsed laser deposition (DPLD) and crossed-beam pulsed laser deposition (CBPLD). Films were studied by means of X-ray reflectometry, wide-angle X-ray scattering and X-ray absorption fine structure experiments. Ballistic simulations of the deposition processes were performed. It is found that adjacent Fe and Al layers are partially intermixed during the deposition, forming Fe-Al transition layers of a few nm in thickness. Both DPLD and CBPLD multilayers have comparable interfaces. In Fe-rich layers, a b.c.c. solid solution is formed. Al-rich layers of approximately 5 nm in nominal thickness are amorphous. DPLD samples have a higher Al content and a significant number of incorporated Al droplets.