Relaxation and local structure changes of a molten TiAl alloy film during quenching have been investigated by molecular dynamics simulations within the framework of embedded atom method (EAM). The details of atom motions are analyzed using mean square displacement (MSD). Accompanying with massive atom rearrangement at a certain quenched temperature and time, local structural patterns are identified by decomposing peaks of pair distribution functions (PDFs) according to the pair analysis(PA) technique. The relaxation factor clearly reveals two relaxation processes involving in slow relaxation and fast relaxation of the quenched liquid TiAl film. Concerning the studied film, the obtained results reveal how quenched temperatures affect local structure changes.