We have grown epitaxial thin films of rare-earth hexa-aluminates on basal plane sapphire from liquid precursors. LnAl11O18 (Ln = Gd3+, Nd3+) films form via the reaction of a perovskite intermediate phase and the sapphire substrate according to LnAlO3 + 5Al2O3 = LnAl11O18. Hexa-aluminate thin films with magnetoplumbite (MP) structure grow epitaxially with (0001)mp ‖(0001)s, 〈1120mp‖〈1010〉s orientation relationship. The a-axis of the film is rotated 30°with respect to the substrate. This rotation results in a smaller mismatch (∼1%) between the two oxygen sublattices. Thermodynamic and kinetic arguments pertaining to magnetoplumbite formation for the smaller Gd3+ cation are presented. These epitaxial thin films are likely to have application in higher temperature ion conduction, catalysis, fluorescence, and as laser host.