For the first time, high surface area nanofibers were synthesized using aluminum isopropoxide monomer with acetic acid as the polycondensation agent in the green solvent, supercritical carbon dioxide (scCO(2)). It was found that the synthesis temperature, pressure, concentration, and acid/alkoxide ratio had a large effect on fiber formation. By optimizing the experimental conditions at 80 degrees C and 6000 psi of scCO(2) using aluminum isopropoxide at a concentration of 0.3 mmol/mL and acid/alkoxide ratio of 10, alumina nanofibers were formed ranging from 11 to 22 nm in diameter and 500 to 1000 nm in length, and with surface areas up to 580 m(2)/g. Lower temperatures gave irregular shaped nanoparticles, while a lower acid/alkoxide ratio (5:1) resulted in the formation of low surface area alumina bars. Increasing pressure led to better separation of the nanofibers and higher surface areas. In addition to the synthesis conditions, the influence of calcination temperature on the structural, textural, and morphological properties of the materials was examined using various physicochemical techniques including electron microscopy, TGA/DTA, powder XRD, FTIR, XPS, and nitrogen adsorption/desorption analysis. The long fibers with high aspect ratios were found to be thermally stable even after calcining at up to 1050 degrees C. The mechanism of fiber formation in scCO(2) is proposed based on a [Al(OH)(CH(3)CO(2))(2)](n) polycondensate backbone.