Solid solutions in the series Cu 2ZnSnS 4xSe 4-4x (CZTSSe) are of interest for PV applications. The purpose of this work was to grow bulk crystalline samples over the entire composition range to allow the Vegard relation (lattice parameter variation with composition) and the systematic behavior of Raman bands to be defined to generate reference data. Samples with 0 ≤ x ≤ 1 were synthesized from the elements and grown into crystalline form from solution in either KCl/NaCl eutectic or elemental Sn. Details of the crystal growth outcomes, including the use of a quartz seed plate to make thick film samples, are described. Ordered kesterite-type material was formed upon crystallization, and X-ray diffraction demonstrated linear Vegard relationships, with the lattice parameters varying with composition as a (Å) = -0.268(3)x + 5.6949(17) and c (Å) = -0.516(6)x + 11.345(3). Raman spectroscopy yielded two dominant peaks, these being kesterite A modes associated with the Se and S modes in CZTSe and CZTS. These varied in wavenumber linearly as ω CZTSe (cm -1) = (44.6 ± 1.6)x + (194.6 ± 0.8) and ω CZTS (cm -1) = (7.1 ± 1.3)x + (329.0 ± 0.8). Crystallization was also shown to promote ordering. The variation of lattice parameters with composition exhibited significant differences from those observed in previous studies. Also, while the Raman S mode behavior differed from previous reports, the Se modes were similar. These differences are discussed.