Ferroelectric solid solutions usually exhibit enhanced functional properties at the morphotropic phase boundary separating two ferroelectric phases with different orientations of polarization. The underlying mechanism is generally associated with polarization rotational instability and the flattened free energy profile. In this work we show that the polarization extensional instability can also be induced at the morphotropic phase boundary beyond the reported polar-nonpolar phase boundary. The piezoelectricity enhanced by this mechanism exhibits excellent thermal stability, which helps to develop high performance piezoelectric materials with good temperature stability.