The influence of uniaxial compressive stress on small-signal relative permittivity and direct piezoelectric coefficient of polycrystalline Li-modified (K0.5Na0.5)NbO3 (0, 2, and 4 mol. % Li) was characterized as a function of temperature from 25 to 450 °C. These data reveal corresponding anomalies in both the dielectric and piezoelectric properties near the well-known structural phase transitions in (KxNa1 − x)NbO3. In particular, increasing stress was found to shift the orthorhombic–tetragonal (TO−T) and tetragonal–cubic (TC) phase boundaries to higher temperatures, thereby stabilizing the lower symmetry phases. Experimental results also show that stress up to a critical value flattens the piezoelectric response below TO−T, above which a monotonic decrease is observed. In contrast, permittivity is increased below TO−T with increasing stress. These results are used to construct a stress–temperature phase diagram of Li-modified (K0.5Na0.5)NbO3.