Fe/Al multilayers are prepared by crossed-beam pulsed laser deposition and investigated by Rutherford backscattering, conversion electron Mössbauer spectroscopy, and transmission electron microscopy. The results are compared to purely ballistic simulations of the deposition process using the TRIDYN4.0 code. It is found that the intermixing of adjacent layers must be described in terms of ballistic mixing followed by chemical mixing. The phase formation in the transition layer between adjacent layers follows the non-equilibrium behavior of Fe/Al in analogy to investigations on mechanically alloyed and ion-beam-mixed Fe/Al. In Fe-rich areas a bcc solid solution is formed. In Al-rich environment an amorphous phase is observed.