Pb(Zr,Ti)O3 (PZT) is used for the various piezoelectric devices owing to its high piezoelectric properties. However, lead (Pb), which is contained in PZT, causes various environment contaminations. (K,Na)NbO3 (NKN) is the most well-known candidate for a lead-free composition to replace PZT. A single crystal has excellent piezoelectric-properties and its properties can be changed by changing the orientation direction. It is hard to fabricate a NKN single crystal due to the sodium and potassium. Thus, (Na,K)NbO3-Ba(Cu,Nb)O3 (NKN-BCuN) is chosen to fabricate the single crystal with relative ease. NKNBCuN pellets consist of two parts, yellow single crystals and gray poly-crystals that contain copper. The area that has a large amount of copper particles may melt at low temperature but not the other areas. The liquid phase may be responsible for the abnormal grain growth in NKN-BCuN ceramics. The dielectric constant and tan δ are measured to be 684 and 0.036 at 1 kHz in NKN-BCuN, respectively. The coercive field and remnant polarization are 14 kV/cm and 20 μC/cm2.