We have fabricated environmental friendly lead-free ferroelectric Na0.5K0.5NbO3 (NKN) and 0.95Na0.5K0.5NbO3–0.05LiNbO3 (0.95NKN-0.05LN) thin films by chemical solution deposition using metal-organic compounds, and studied the effects of LN substitution through the dielectric and ferroelectric properties. The small amount of LN substitution for NKN thin film led to a marked improvement in leakage current properties at the high electric field region. Furthermore, the 0.95NKN-0.05LN thin film (350 nm) displayed clear ferroelectricity with well saturated P-E hysteresis loop with 2Pr and 2Ec values of 19.5 μC/cm2 and 91 kV/cm, respectively. The 0.95NKN-0.05LN films will be interesting for applications in lead-free ferroelectric and piezoelectric devices.