A facile hydrothermal route was adopted for synthesis of lead-free piezoceramics (K, Na)NbO3 powders. The influences of temperature and KOH/NaOH concentration on the resultant powders were investigated. Although two similar perovskite phases appeared when K/Na ratio tended toward 1:1, the two-phase coexistence tendency was weakened by increasing hydrothermal reaction temperature, and consequently only one phase could be obtained after spark plasma sintering. Reasonably good ferroelectric and piezoelectric properties were obtained for the samples after postannealing, whose piezoelectric constant (d33) reached 135 pC/N. The optimal remnant polarization (Pr) and mechanical quality factor (Qm) were 26.2 μC/cm2 and 164, respectively, which were both twice as much as those of the samples using powders prepared from solid-state reaction.