Single crystals of (1 - x)BaTiO3 + xNaNbO(3) (BTNN) for x = 0.84 were obtained by high temperature solution growth using Na2B4O7 as solvent. The room temperature crystal structure of BTNN 16/84-phase was determined from X-ray single crystal diffraction data, in the tetragonal system with space group P4bm. The refinement from 246 independent reflections led to the following parameters: a = b = 5.5845(3) angstrom, c = 3.9453(2) angstrom, V = 123.041(11) angstrom(3), Z = 2, with final cR(wp) = 0.150 and R-B = 0.041. The structure of BTNN 16/84-phase can be described as a three-dimensional framework built up from (Nb-Ti)O-6 octahedra with Na and Ba in the dodecahedral site of perovskite-like type. Some mm(3)-sized crystals have been selected and various dielectric measurements (ferroelectric, pyroelectric, and piezoelectric) have been performed. Transition from paraelectric to ferroelectric state at around 460 K has been observed to be in good agreement with ceramics of closer composition. Dielectric, piezoelectric and pyroelectric measurements on crystal confirm the ferroelectric behaviour of BTNN 16/84. (C) 2009 Elsevier Ltd. All rights reserved.