Na5Ti3O3F11 was prepared by the microwave assisted method, and presents a chiolite related structure with cell parameters a=10.5016(5), b=10.4025(5), and c=10.2911(5)Å and Cmca (n° 64) space group. From solvothermal synthesis at 100 °C the cryolite Na3-δVO1-δF5+δ was prepared, which crystallizes in the monoclinic system with a= 5.5403(2), b=5.6804(2), c=7.9523(2)Å, β= 90.032(7)° cell parameters and P21/n (n°14) space group. Under similar synthesis conditions but with higher HF concentration the chiolite-type phase Na5-δV3F14 was achieved, which exhibits a= 10.5482(2), b= 10.4887(1) and c= 10.3243(1) Å cell parameters and Cmc21 (n° 36) space group. A single crystal also having the chiolite structure was synthesized at 200 °C which exhibits tetragonal symmetry (a= 7.380(3) and c=10.381(11) Å and space group P42212 (n° 94)). Bond valence sum indicates that it contains V4+ and therefore can be formulated as Na5V3O3F11.