We report solvothermal preparations of nanocrystalline CuIn1-xAlxSe2 materials prepared from the reaction of Se, CuX2 (X = Cl− or stearate), InCl3, and Al(oleate)3 in refluxing oleylamine for 30 minutes to 3 hours. Scanning electron microscopy (SEM) images reveal morphologies consisting of hexagonal plates (100-400 nm diameter) with smaller isomorphic nodules. Micro-Raman spectroscopy, x-ray diffraction, and optical bandgap data are consistent with Al3+ incorporation into the chalcopyrite structure. For aluminum-containing reactions, product Al/(In+Al) ratios are estimated to be between 0.15 and 0.35 regardless of the indium-aluminum stoichiometry employed in the reaction. When Se is added to the reaction last, the reaction pathway involves an early-formed Cu2-xSe(s) intermediate that appears to react with In- and Al-containing species simultaneously. This intermediate is avoided when heating InCl3, Al(oleate)3, and Se together prior to Cu addition, but the final product includes Se contamination that must be removed or reacted by annealing.