Ferroelectric K3Li2Nb5O15 (KLN-1) crystals have been grown by the top-seeded solution growth method from pure, Na+, Rb+ and Cs+ doped melt. The impact of alkali additives was assessed all over the entire pulling range by investigating the variation of the structural and physical properties by using spectroscopic and dielectric methods. The incorporation of alkali homologs has been correlated with their ionic radii: Na+ ions were found to enter both Li and K sites with high segregation coefficient (k∼1.6), Rb+ ions were detected only at K sites (k∼0.34) and Cs+ ions practically did not incorporate into the lattice (k∼0.12). Alkali additives have been found to play a dual role in the growth process by affecting the crystallization temperature and promoting the K and Li site occupancy. By decreasing the crystallization temperature the Cs2O additive reduced the concentration both of the antisite Nb ions at Li site and that of alkali vacancies; therefore it can be considered as a promising fluxing agent in the growth of KLN crystals.