The synthetic details of a novel potassium gallosilicate natrolite with Si/Ga = 1.28, denoted PST-1, are described. The presence of K(+) and Ga with well-defined levels of concentration in the synthesis mixture is essential for directing its crystallisation. PST-1 transforms rapidly into TNU-6 under hydrothermal conditions, behaviour that contrasts sharply with its very high thermal and hydrothermal stability, which is unusual for a material of such a high Ga content. These stability issues are discussed and rationalized based on chemical composition, likely violations of Loewenstein's rule and the temperature of dehydration of as-made K-PST-1. The crystal structure of TNU-6 has been resolved through the combined use of synchrotron X-ray and electron diffraction data; it has the BaFeGaO(4) structure type with an additional radical 3a x radical 3a "GeAlO(4)" superstructure that arises from tilting of some of the tetrahedral units in all of the 6-rings.