In order to develop lead-free piezo-/ferroelectric materials, single crystals of 0.98K(0.8)Na(0.2)NbO(3)-0.02LiNbO(3) (KNN-LN) have been grown in the perovskite structure using the high-temperature solution growth method. Dielectric measurements reveal structural phase transitions at T-C (cubic to tetragonal)=411 degrees C and TO-T (tetragonal to orthorhombic)=189 degrees C, respectively, and an additional phase transition at a lower temperature of -78 degrees C which corresponds to the transition from the orthorhombic to a rhombohedral phase. Single crystal structural refinements based on X-ray diffraction data indicate that there are no oxygen octahedral tilts present at room temperature and at -103 degrees C, which suggests that the crystal is K-rich. Composition analysis by energy dispersive spectroscopy and laser ablation - inductively coupled plasma - mass spectrometry confirms the K-rich composition. A vapour transport equilibration technique is successfully developed to optimise the composition of the as-grown crystals by enriching the Li-content and it is demonstrated to be a viable approach to increase the Li-concentration of KNN-LN and other piezo-/ferroelectric crystals.