The phase boundary structure of (K,Na)NbO3 piezoelectric ceramic was modified by doping with Bi(Na,K,Li)ZrO3 and BiGaO3 through normal solid-state sintering. Rietveld refinements by X-ray diffraction revealed that the Bi(Na,K,Li)ZrO3/BiGaO3 co-doping in (K,Na)NbO3 led to a multi-phase structure at room-temperature, effectively moving the rhombohedral-orthorhombic (R-O) and orthorhombic-tetragonal (O-T) polymorphic phase transition temperatures close to the room temperature region. Increased levels of doping also generated a structural transition, i.e., triphasic R-O-T to diphasic R-T (T-rich) and finally to R-T (R-rich), contributing to shrinkage of the O phase as well as the increase of R phase fraction. A sensitive influence of the BiGaO3 doping (0.001 mole fraction level) on the structural properties such as the phase and microstructure was shown, resulting from the effect of the super-tetragonal structure of BiGaO3. The d33 property was strongly dependent on the phase and its volume fraction, in addition to the grain sizes. Eventually, enhanced and balanced properties of the piezoelectric coefficient and Curie temperature (d33 = 309 pC/N, TC = 343 °C) were obtained when the doped ceramic had a T-rich (86%) R-T structure.