Phase diagrams of BiFeO3-BaTiO3 (BF–BT) thin films were constructed via thermodynamic model calculation, as well as their electrical properties. The calculated morphotropic phase boundary (MPB) of BF–BT thin films without strain is located near the composition of 0.663BF–0.337BT, which agrees well with the experimental results of reported BF–BT ceramics (between 0.66BF–0.34BT and 0.71BF–0.29BT). The permittivity, tunability and [Formula: see text] of BF–BT thin films on Si substrates are higher than those on SrTiO3 (ST) plates, which are also in accordance with the measured data in the literature. Further calculation indicates that 0.7BF–0.3BT and 0.6BF–0.4BT thin films can achieve enormous piezoelectric coefficient [Formula: see text] ([Formula: see text]1200 and [Formula: see text]1000 pm/V, respectively) by selecting the substrates with the TEC respectively of 0.3 and 3.1 × 10[Formula: see text]/[Formula: see text]C, because of the phase transition from aa phase to rhombohedral phase. Such results help to clarify the phase diagrams of BF–BT thin films, implying that huge [Formula: see text] can be achieved by choosing the composition near MPB on the substrates with small TEC.