We report here the use of liquid-feed flame spray pyrolysis (LF-FSP) to produce a series of nanopowders along the CoOx–Al2O3 tie line. The process is a general aerosol combustion synthesis route to a wide range of lightly agglomerated oxide nanopowders. The materials reported here were produced by aerosolizing ethanol solutions of alumatrane [Al(OCH2CH2)3N] and a cobalt precursor, made by reacting Co(NO3)2·6H2O crystals with propionic acid. The compositions of the as-produced nanopowders were controlled by selecting the appropriate ratios of the precursors. Nine samples with compositions (CoO)y(Al2O3)1−y, y=0−1 along the CoOx–Al2O3 tie line were prepared and studied. The resulting nanopowders were characterized by X-ray fluorescence, BET, scanning electron microscopy, high-resolution transmission electron micrographs, X-ray diffraction (XRD), thermogravimetric analysis (TGA), and FTIR. The powders typically consist of single-crystal particles <40 nm diameter and specific surface areas (SSAs) of 20–60 m2/g. XRD studies show a gradual change in powder patterns from -Al2O3 to Co3O4. The cobalt aluminate spinel phase is observed at stoichiometries (21 and 37 mol%) not seen in published phase diagrams, likely because LF-FSP processing involves a quench of >1000°C in microseconds frequently leading to kinetic rather than thermodynamic products. Likewise, the appearance of Co3O4 rather than CoO as the end member in the tie line is thought to be a consequence of the process conditions. TGA studies combined with diffuse reflectance FTIR spectroscopic studies indicate that both physi- and chemi-sorbed H2O are the principal surface species present in the as-processed nanopowders. The only sample that differs is Co3O4, which has some carbonate species present that are detected and confirmed by a sharp mass loss event at ∼250°C. The thermal behavior of the high cobalt content samples differs greatly from the low cobalt content samples. The latter behave like most LF-FSP-derived nanopowders exhibiting typical 1%–4% mass losses over the 1400°C range due mostly to loss of water and some CO2. The high cobalt content samples exhibit a sharp mass loss event that can be attributed to the decomposition of Co3O4 to CoO.