We have investigated the effect of Bi-excess surface layers of stoichiometric BiFeO3 thin films prepared by chemical solution deposition. A stoichiometric BiFeO3 thin film with both the Bi-excess top and bottom surface layers shows improved crystallinity with the remanent polarization of 65 μC/cm2 at 80 K, which is larger than BiFeO3 film prepared by the same process using stoichiometric solution. These results are attributed to the reduction of the imperfect crystal at the interface between BiFeO3 film and electrode. Stoichiometric BiFeO3 thin film with Bi-excess top and bottom surface layers also reserves the magnetic property of stoichiometric film. Stoichiometric BiFeO3 thin films with Bi-excess surface layers are an effective way to obtain good multiferroic properties.