Tris(benzoylpivaloylmethanato)aluminium(III) and its ring-substituted derivatives, Al(pX-BPM) (p means the para position in the phenyl ring; X is H, F, Cl, NO2, MeO, Me) have been synthesized and the forms less soluble in an ethanol-benzene mixture have been examined by means of elemental analysis, HPLC, H-1 NMR, IR and Raman spectroscopy, and thermogravimetry. H-1 NMR spectra show that these forms adopt mer configuration. The chelates where X is H, F, Cl are volatile, but those where X is Me, MeO, NO2 decompose in the 350-450-degrees-C temperature range. IR data suggest inequivalence of the two CO bonds in each of the coordinated ligands. The four bands were assigned to Al-O vibration on the basis of the metal effect.