In this study, the traditional hot rolling to fabricate Al/Ti laminated metal composites (LMCs) was improved by using a pre-rolling diffusion process. The effect of the pre-rolling diffusion on microstructure and mechanical properties of Al/Ti LMCs were investigated by various methods, such as optical microscope (OM), scanning electron microscope (SEM), energy dispersive spectrometer (EDS) and tensile tests. The results show that, with increasing diffusion temperature, the thickness in diffusion layer was increased and the mechanical properties of LMCs were improved obviously, which was attributed to the optimized interfacial structure after diffusion process. In addition, the formation of TiAl3 intermetallic compounds (IMCs) was detected in the bonding interface, which played an important role in improving the mechanical properties for Al/Ti LMCs. The predicted results of stress-strain curves from rule of mixture (ROM) indicated that, there existed an extra interfacial strengthening in Al/Ti LMCs beside the mechanical properties provided by the contribution of constituent layers. The pre-rolling diffusion process is effective for the optimization of interfacial structure and improvement of mechanical properties in Al/Ti LMCs.