A novel method is reported for the preparation of phase-pure beta "-(Na) alumina by the gel to crystallite conversion technique. Coarse gels of hydrated alumina, Al2O3 . Y H2O (80 < Y < 120), were reacted with sodium hydroxide solution in ethanol, yielding crystalline NaxAlOx(OH)(3-x) (0.17 < x < 0.23) having the gibbsite structure with inserted sodium ions. Thermal decomposition of this precursor above 573 K yielded the intermediate NaxAlO1+x(OH)(1-x) with the boehmite structure. At higher temperatures this intermediate gave rise to gamma-alumina, NaxAl2O3-x(OH)(3x) and NaAl7/3O4 with the defect spinel structure. It is proposed that because of the cubic close packing of oxygen ions present in the intermediate alumina, formation of beta "-alumina takes place above 1273 K as a continuous solid-state process with minimal rearrangement of the close packed oxide ions. The beta "-alumina phase thus formed is free of intergrowths of the beta-phase, as revealed by HREM and is stable up to near-melting conditions.