The [(Pb 0.90 La 0.10 )Ti 0.975 O 3 /PbTiO 3 ] n (PLT/PT) n (n=1–6) multilayer thin films were deposited on the PbO x (100)/Pt/Ti/SiO 2 /Si substrates by RF magnetron sputtering method. The layer thickness of PbTiO 3 in one periodicity kept unchanged, and the layer thickness of (Pb 0.90 La 0.10 )Ti 0.975 O 3 is varied. The electrical properties of the (PLT/PT) n multilayer thin films were investigated as a function of the periodicity (n) and the orientation. The studied results show that the PbO x buffer layer results in the (PLT/PT) n films’ (100) orientation, and the (100)-oriented (PLT/PT) n multilayer thin films with n=2 exhibit better pyroelectric properties and ferroelectric behavior than those of (PLT/PT) n films with other periodicities and orientations. The underlying physical mechanism for the enhanced electrical properties of (PLT/PT) n multilayer thin films was carefully discussed in terms of the periodicities and orientations.