A monoclinic ferroelectric phase with space group Pm has been discovered in lead-free (K0.5Na0.5)NbO3-5%LiNbO3 solid solution ceramics by high energy synchrotron x-ray powder diffraction measurements. At ambient temperature, the lattice parameters of this monoclinic structure were (a(m), b(m), c(m); beta) = (4.015 angstrom, 3.944 angstrom, 3.987 angstrom; 90.34 degrees). This monoclinic phase transformed to a tetragonal (P4mm) one on heating between 340 K and 360K. The results demonstrate the presence of structurally bridging low symmetry monoclinic phase in (K0.5Na0.5)NbO3-x%LiNbO3 solid solution system: indicating a means to achieve high piezoelectricity in Pb-free systems via domain engineering. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4716027]